CN102138703B - Top modified transitional metal carbon hollow pipe material, and preparation method and application thereof - Google Patents
Top modified transitional metal carbon hollow pipe material, and preparation method and application thereof Download PDFInfo
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- CN102138703B CN102138703B CN 201110002999 CN201110002999A CN102138703B CN 102138703 B CN102138703 B CN 102138703B CN 201110002999 CN201110002999 CN 201110002999 CN 201110002999 A CN201110002999 A CN 201110002999A CN 102138703 B CN102138703 B CN 102138703B
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Abstract
The invention relates to a top modified transitional metal carbon hollow pipe material, and a preparation method and application thereof. The preparation method comprises the following steps of: placing a multi-hydroxyl polymer and an organic compound of transitional metal into a stainless steel high-pressure kettle; sealing the kettle; placing the kettle into a high-temperature furnace and heating the kettle to be from room temperature to 320 to 500 DEG C within 30 to 55 minutes; preserving the heat for 9 to 15 hours; cooling to room temperature; leaching with absolute ethanol; leaching with distilled water to remove impurities; and performing vacuum drying to obtain the material in which the transitional metal iron, cobalt or nickel is gathered at one end of a carbon hollow pipe. The material has high adsorption property; the preparation method is simple; the preparation condition is easy to control; and the top modified transitional metal carbon hollow pipe has high preparation reproducibility.
Description
Technical field
The present invention relates to a kind of carbon hollow pipe material and the application in cigarette thereof, belong to technical field of tobacco.
Background technology
Smoking is the problem that people generally are concerned about with health, and the harmful components such as determination of hydrogen cyanide in mainstream cigarette smoke receive much concern on the impact of health.Therefore reducing the harmful components in the flue gas, alleviate harm of smoking, improve quality and the security of cigarette product, is the tobacco business problem needing to overcome, and the low hazard cigarette of high-quality and safety has become the development trend of international cigarette.The research work in early stage shows: because the source of harmful constituents in cigarette flue gas is complicated, fall Jiao and can only partly suppress harmful components in the cigarette smoke, only can't effectively remove harmful substances in flue gas from the tar content that reduces cigarette, it is very necessary therefore carrying out reduction work for a certain harmful components in the flue gas.The carbon hollow pipe is as a kind of material of emerging development, owing to have special structure, causes it to have many physics and chemistry performances different from traditional material and application prospect widely thereof.This material has following features: hollow hole structure, low-density, high porosity, large specific surface and can allow liquid or gas selectively to pass through have simultaneously excellent absorption and catalytic performance, so the carbon hollow pipe is widely used in various function and structure materials.
The carbon hollow pipe that patent CN101618867A discloses a kind of transition metal ions is the carbon hollow material, this kind material distils fast and contains growth promoter of sulfur by Organometal compound catalyst and fully mixes under gaseous state, under carrying secretly, buffer gas enters again the reaction zone reaction, what this patent obtained is the carbon hollow material that metallic particles is modified around CNT, this kind material preparation method complexity, preparation condition is harsh.
Summary of the invention
The purpose of this invention is to provide a kind of top and modify carbon hollow pipe material of transition metal and its preparation method and application.
The technical scheme that the present invention takes is:
The carbon hollow pipe material of transition metal is modified on the top, and transition metal iron, cobalt or nickel are gathered in an end of carbon hollow pipe.
The preparation method of the carbon hollow pipe material of transition metal is modified on described top, and step is as follows:
Organic compound and the polyhydroxylated polymer of transition metal are put into stainless steel autoclave, and sealing is placed in the high temperature furnace and is warmed up to 320-500 ℃ by room temperature in 30-55min, and keeps 9-15 hour in this temperature; After being cooled to room temperature, use first absolute ethyl alcohol drip washing, remove impurity with distilled water drip washing again, then vacuum drying namely obtains the carbon hollow pipe that transition metal is modified on the top.
Described polyhydroxylated polymer is 2: 1～6: 1 with the quality of the organic compound of transition metal than scope.
The organic compound of described transition metal is oxalates or the acetate of transition metal.
Described polyhydroxylated polymer is polyvinyl alcohol or polyethylene glycol.
The carbon hollow pipe material that transition metal is modified on described top in cigaratte filter as the application of filtering material.
Contain described top in the filter tip and modify the cigarette of the carbon hollow pipe material of transition metal.
The advantage of the carbon hollow pipe material of transition metal is modified on top of the present invention: high porosity, large specific surface and can allow liquid or gas selectively to adsorb, because carbon hollow pipe material one end opening of transition metal is modified on the top, the adorned transition metal sealing of one end, this structure makes it have special absorption property, can be used as simultaneously the carrier of transition metal, when the transition metal is modified carbon hollow pipe material one end, because transition metal particles enters nanometer scale, the size confinement will cause quantum effect, cause it to have the performances such as excellent absorption and catalysis, can effectively reduce harmful components hydrogen cyanide in the cigarette mainstream flue gas.
The advantage of the carbon hollow tube preparation method for material of transition metal is modified on top of the present invention: the preparation method is simple, and preparation condition is easy to control, and the CNT of the transition metal that the top is modified prepares favorable reproducibility.
Contain described top in the filter tip of the present invention and modify the cigarette of the carbon hollow pipe material of transition metal, can improve the mouth rod to the adsorption effect of harmful substances in flue gas hydrogen cyanide, reduce harmful constituents in cigarette flue gas hydrogen cyanide content, the cigarette style remains unchanged, and improves the security of cigarette smoking.Experimental result shows: added the cigarette filter tip that the carbon hollow pipe of iron, cobalt, nickel is modified on the top, can obviously reduce the content of harmful substances in flue gas hydrogen cyanide, wherein the reduction hydrogen cyanide effect of the carbon hollow pipe of top modification iron is best, the addition of modifying the carbon hollow pipe of iron along with the top increases, the amount of hydrogen cyanide reduces in the flue gas, and the content of hydrogen cyanide reduces 14.6～43% in the flue gas.
Description of drawings
Fig. 1 is the carbon hollow pipe pattern analysis chart that transition metal is modified on the top, and (A) the SEM photo of the carbon hollow pipe of iron is modified on the top, and (B) the SEM photo of the carbon hollow pipe of cobalt is modified on the top, and (C) the SEM photo of the carbon hollow pipe of nickel is modified on the top;
Fig. 2 is the carbon hollow pipe material thermogravimetric analysis figure that transition metal is modified on the top;
Fig. 3 contains the composite cigarette filter tip structure chart that the carbon hollow pipe material of transition metal is modified on described top; Wherein: 1 is tow, and the 2 carbon hollow pipe materials for top modification transition metal add layer.
The specific embodiment
It is pure that all reagent are analysis, available from Shanghai traditional Chinese medicines group.Automatic analyzer AA3 (BranLuebbe, Germany), H-7000 type transmission electron microscope (Hitachi, Ltd, Japan), high resolution transmission electron microscopy JEM-2100 (electronics corporation, Japan), smoking machine SM450 (Cerulean company, Britain).
The carbon hollow pipe that iron is modified on the top synthesizes: after 25 gram polyvinyl alcohol and 10 gram ferric oxalates evenly mix, insert in the stainless steel autoclave, put into high temperature furnace after the sealing, in 40min, be warmed up to 320 ℃ by room temperature, and under this temperature, kept 10 hours, after being cooled to room temperature, use first absolute ethyl alcohol drip washing, remove impurity with distilled water drip washing again, then 40 ℃ of vacuum drying 4 hours, namely obtain the top and modify the carbon hollow pipe of iron, pattern is seen Fig. 1 (A).
The carbon hollow pipe that iron is modified on the top synthesizes: after 50 gram polyvinyl alcohol and 20 gram ferric oxalates evenly mix, insert in the stainless steel autoclave, put into high temperature furnace after the sealing, in 30min, be warmed up to 370 ℃ by room temperature, and under this temperature, kept 15 hours, be cooled to room temperature after, use first absolute ethyl alcohol drip washing, remove impurity with distilled water drip washing again, then 40 ℃ of vacuum drying 4 hours, namely obtain the carbon hollow pipe that iron is modified on the top.
Embodiment 3
The carbon hollow pipe that iron is modified on the top synthesizes: after 30 gram polyethylene glycol and 12 gram ferric oxalates evenly mix, insert in the stainless steel autoclave, put into high temperature furnace after the sealing, in 30min, be warmed up to 350 ℃ by room temperature, and under this temperature, kept 12 hours, be cooled to room temperature after, use first absolute ethyl alcohol drip washing, remove impurity with distilled water drip washing again, then 40 ℃ of vacuum drying 4 hours, namely obtain the carbon hollow pipe that iron is modified on the top.
Embodiment 4
The carbon hollow pipe that nickel is modified on the top synthesizes: 30 gram polyvinyl alcohol and 6 gram nickel oxalate presomas are put into stainless steel autoclave, and sealing is placed in the high temperature furnace and is warmed up to 420 ℃ by room temperature in 40min, and keeps 12 hours in this temperature.After being cooled to room temperature, use first absolute ethyl alcohol drip washing, remove impurity with distilled water drip washing again, then 40 ℃ of vacuum drying 4 hours, namely obtain the carbon hollow pipe that nickel is modified on the top, pattern is seen Fig. 1 (C).
Embodiment 5
The carbon hollow pipe that nickel is modified on the top synthesizes: 50 gram polyvinyl alcohol and 8 gram nickel oxalate presomas are put into stainless steel autoclave, and sealing is placed in the high temperature furnace and is warmed up to 470 ℃ by room temperature in 50min, and keeps 10 hours in this temperature.After being cooled to room temperature, use first absolute ethyl alcohol drip washing, remove impurity with distilled water drip washing again, then 40 ℃ of vacuum drying 4 hours, namely obtain the carbon hollow pipe that nickel is modified on the top.
Embodiment 6
The carbon hollow pipe that nickel is modified on the top synthesizes: 40 gram polyethylene glycol and 7 gram nickel oxalate presomas are put into stainless steel autoclave, and sealing is placed in the high temperature furnace and is warmed up to 450 ℃ by room temperature in 50min, and keeps 10 hours in this temperature.After being cooled to room temperature, use first absolute ethyl alcohol drip washing, remove impurity with distilled water drip washing again, then 40 ℃ of vacuum drying 4 hours, namely obtain the carbon hollow pipe that nickel is modified on the top.
Embodiment 7
The carbon hollow pipe that cobalt is modified on the top synthesizes: 25 gram polyvinyl alcohol and 4 gram cobalt oxalate presomas are put into stainless steel autoclave, and sealing is placed in the high temperature furnace and is warmed up to 420 ℃ by room temperature in 45min, and keeps 11 hours in this temperature.After being cooled to room temperature, use first absolute ethyl alcohol drip washing, remove impurity with distilled water drip washing again, then 40 ℃ of vacuum drying 4 hours, namely obtain the carbon hollow pipe that cobalt is modified on the top, see Fig. 1 (B).
Embodiment 8
The carbon hollow pipe that cobalt is modified on the top synthesizes: 35 gram polyethylene glycol and 6 gram cobalt oxalate presomas are put into stainless steel autoclave, and sealing is placed in the high temperature furnace and is warmed up to 500 ℃ by room temperature in 55min, and keeps 9 hours in this temperature.After being cooled to room temperature, use first absolute ethyl alcohol drip washing, remove impurity with distilled water drip washing again, then 40 ℃ of vacuum drying 4 hours, namely obtain the carbon hollow pipe that cobalt is modified on the top.
Performance test:
The carbon hollow pipe pattern that iron, cobalt, nickel are modified in the top of gained adopts transmission electron microscope (SEM) to carry out analysis and characterization (such as Fig. 1), and its diameter mainly concentrates on 60-120nm, and length range can reach several microns tens microns.
In air, the carbon hollow pipe of the top being modified iron, cobalt, nickel has carried out respectively thermogravimetric analysis, and the heat endurance of the carbon hollow pipe of discovery top modification nickel is best, when temperature reaches 630 ℃ to just observing obvious weightlessness (seeing Fig. 2).The carbon hollow pipe heat endurance of top modification cobalt is taken second place, and obviously weightless temperature is 550 ℃.It is the poorest that the carbon hollow pipe heat endurance of iron is modified on the top, and obviously weightless temperature is 430 ℃.The weightless scope of carbon hollow pipe that iron, cobalt, nickel are modified in the top is 430-630 ℃, can stable existence 430 ℃ before in air, and carbon hollow pipe of this explanation top modification iron, cobalt, nickel has good heat endurance.
Accurately take by weighing respectively 0.005 gram, 0.010 gram, 0.015 gram and 0.020 gram top and modify the carbon hollow pipe of iron, cobalt, nickel, be compound in the filter tip of finished cigarettes, make the composite filter tip (seeing Fig. 3) of new cigarette.
The analyzing and testing of hydrogen cyanide in the cigarette smoke: based on isonicotinic acid and 1,3-dimethyl barbituric acid color development system is 600nm photometric detection hydrogen cyanide on the Continuous Flow Analysis instrument, with the hydrogen cyanide in the continuous flow method detection cigarette mainstream flue gas, the method safety and environmental protection, simple to operate, highly sensitive, good reproducibility.
(1) the carbon hollow pipe of different metal modification reduces effect to hydrogen cyanide in the flue gas
Accurately take by weighing respectively 0.010 gram top and modify iron, cobalt, three kinds of carbon hollow pipes of nickel as the additive of cigarette filter tip, be made into composite filter tip, as shown in Figure 3.The content that adds hydrogen cyanide in every cigarette smoke modifying iron, cobalt, three kinds of carbon hollow pipes of nickel Combined roll cigarette holder rod in the top sees Table 1, can draw the top from this table and modify iron, cobalt, three kinds of carbon hollow pipes of nickel the content that reduces hydrogen cyanide the flue gas is had positive effect, and the carbon hollow pipe that iron is modified on the top reduces hydrogen cyanide best results in the flue gas.Infer thus: the carbon hollow pipe of iron is modified on the top because the mating capability of iron ion and CN-is stronger, causes the effect of the hydrogen cyanide in its absorption flue gas better.
Table 1: add hydrogen cyanide content in the carbon hollow pipe flue gas of modifying different metal in the top in the filter tip
| Title | Hydrogen cyanide (ug/ props up) |
| Original cigarette | 139.3 |
| Add the carbon hollow pipe composite filter tip cigarette that iron is modified on 0.010 gram top | 99.6 |
| Add the carbon hollow pipe composite filter tip cigarette that cobalt is modified on 0.010 gram top | 109.4 |
| Add the carbon hollow pipe composite filter tip cigarette that nickel is modified on 0.010 gram top | 119.6 |
The carbon hollow pipe of iron is modified to hydrogen cyanide reduction impact in the flue gas in the top of (2) adding different amounts
Accurately take by weighing respectively 0.005 gram, 0.010 gram, 0.015 the carbon hollow pipe of iron is modified on gram and 0.020 gram top, be compound in the filter tip of finished cigarettes, the content that records its hydrogen cyanide sees Table 2, can draw the addition increase of modifying the carbon hollow pipe of iron along with the top, the content of hydrogen cyanide reduces successively in the flue gas, the carbon hollow pipe of iron is modified in this explanation along with the top quantity increases, the ironwork point quantity of hydrogen cyanide increases in the absorption flue gas, hydrogen cyanide is along with the addition of the carbon hollow pipe of top modification iron increases and reduces in the flue gas, after but the carbon hollow pipe addition of modifying iron when the top restrains above 0.015, add the more carbon hollow pipe of volume top modification iron, will cause the resistance to suction of cigarette to become large, affect the suction of cigarette and inhale flavor.Consider: the addition of the carbon hollow pipe of every cigarette 0.015 gram top modification iron is best for the content that reduces flue gas hydrogen cyanide.
Table 2: add hydrogen cyanide content in the carbon hollow pipe flue gas of modifying iron in different tops of measuring in the filter tip
| Title | Hydrogen cyanide (ug/ props up) |
| Original cigarette | 139.3 |
| Add the carbon hollow pipe composite filter tip cigarette that iron is modified on 0.005 gram top | 110.8 |
| Add the carbon hollow pipe composite filter tip cigarette that iron is modified on 0.010 gram top | 99.6 |
| Add the carbon hollow pipe composite filter tip cigarette that iron is modified on 0.015 gram top | 90.5 |
| Add the carbon hollow pipe composite filter tip cigarette that iron is modified on 0.020 gram top | 78.9 |
The carbon hollow pipe of iron is modified on the comparative study top, the carbon hollow pipe of cobalt is modified on the top, three kinds of carbon hollow pipes of carbon hollow pipe of nickel are modified as the composite tip stick of the additive of cigarette filter tip in the top, can both obviously improve cigarette filter to hydrogen cyanide harmful components adsorption effect, effectively reduce hydrogen cyanide content in the cigarette smoke, find simultaneously the carbon hollow pipe of top modification iron, because iron ion has stronger and CN-coordination ability, it reduces the best results of harmful substances in flue gas hydrogen cyanide, the carbon hollow pipe of modifying iron along with the top increases, the content of harmful substances in flue gas hydrogen cyanide reduces gradually, minimum minimizing 43%, thereby add the carbon hollow pipe that iron is modified on the top to be used for elective reduction harmful substances in flue gas hydrogen cyanide in the cigarette composite tip stick content, having broad application prospects aspect the cigarette smoke lowering harm and decreasing coking.
Claims (6)
1. the carbon hollow pipe material of transition metal is modified on the top, it is characterized in that transition metal iron, cobalt or nickel are gathered in an end of carbon hollow pipe.
2. the carbon hollow tube preparation method for material of transition metal is modified on top according to claim 1, it is characterized in that step is as follows:
The oxalates of transition metal or acetate and polyhydroxylated polymer are put into stainless steel autoclave, and sealing is placed in the high temperature furnace and is warmed up to 320-500 ℃ by room temperature in 30-55min, and keeps 9-15 hour in this temperature; After being cooled to room temperature, use first absolute ethyl alcohol drip washing, remove impurity with distilled water drip washing again, then vacuum drying namely obtains the carbon hollow pipe material that transition metal is modified on the top.
3. the preparation method of the carbon hollow pipe material of transition metal is modified on top according to claim 2, it is characterized in that described polyhydroxylated polymer is 2:1 ~ 6:1 with the quality of the organic compound of transition metal than scope.
4. the preparation method of the carbon hollow pipe material of transition metal is modified on top according to claim 2, it is characterized in that described polyhydroxylated polymer is polyvinyl alcohol or polyethylene glycol.
Top claimed in claim 1 modify transition metal carbon hollow pipe material in cigaratte filter as the application of filtering material.
6. contain top claimed in claim 1 in the filter tip and modify the cigarette of the carbon hollow pipe material of transition metal.
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| CN108523217A (en) * | 2018-06-08 | 2018-09-14 | 滁州卷烟材料厂 | A kind of cigarette filter rod with tar reduction flavouring performance |
| CN110724491B (en) * | 2019-09-10 | 2020-09-11 | 北京石墨烯技术研究院有限公司 | Wave absorbing agent, preparation method thereof and wave absorbing material |
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| WO2006115486A1 (en) * | 2005-04-22 | 2006-11-02 | Seldon Technologies, Llc | Article comprising carbon nanotubes and method of using the same for purifying fluids |
| CN101239715A (en) * | 2008-03-06 | 2008-08-13 | 广州大学 | Diacetyl cellulose-carbon nano-tube derivatives, preparation method and use thereof |
| CN101692934A (en) * | 2009-10-22 | 2010-04-14 | 湖南中烟工业有限责任公司 | Additive for lowering harmful constituents in cigarette flue gas and cigarette thereof |
| CN101992063A (en) * | 2010-09-30 | 2011-03-30 | 山东大学 | Method for preparing carbon nano hollow grid capable of adsorbing harmful ingredients in tobacco |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006115486A1 (en) * | 2005-04-22 | 2006-11-02 | Seldon Technologies, Llc | Article comprising carbon nanotubes and method of using the same for purifying fluids |
| CN101239715A (en) * | 2008-03-06 | 2008-08-13 | 广州大学 | Diacetyl cellulose-carbon nano-tube derivatives, preparation method and use thereof |
| CN101692934A (en) * | 2009-10-22 | 2010-04-14 | 湖南中烟工业有限责任公司 | Additive for lowering harmful constituents in cigarette flue gas and cigarette thereof |
| CN101992063A (en) * | 2010-09-30 | 2011-03-30 | 山东大学 | Method for preparing carbon nano hollow grid capable of adsorbing harmful ingredients in tobacco |
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