WO2012034261A1 - Hollow carbon sphere material, production method thereof and cigarette containing the same - Google Patents

Abstract

Disclosed are a hollow carbon sphere material, a production method thereof, and a cigarette containing the same. The hollow carbon sphere material is produced by the following method, which comprises: adding polyhydric organic compound which acts as carbon source and NaN₃ as catalyst into an autoclave in a certain ratio; sealing the autoclave and placing it into a high temperature furnace; rising the temperature of the furnace from room temperature to 400 ~ 420℃ within 40 min., and then holding the temperature for 350 ~ 450 min.; cooling, collecting, washing, filtering and drying are then followed to obtain the hollow carbon sphere material. The diameter distribution of the hollow carbon sphere material thus obtained stays between 100 to 300 nm mainly, and the thickness of the shell of the hollow carbon sphere is about 20 nm. The graphitization degree of the obtained hollow carbon sphere material is low, and the thermal stability proved to be good by thermogravimetric analysis, which ensures its stability in air at not more than 500℃. When the hollow carbon sphere material is used as a filter layer in the cigarette filter-tip, the contents of tar and ammonia can be effectively decreased.

Description

 Carbon hollow sphere material, preparation method thereof and cigarette containing the same

 The present invention relates to a carbon hollow sphere material, and more particularly to a carbon hollow sphere material that can be used for mouthpiece filtration.

Background technique

 Smoking and health are common concerns. The harmful effects of harmful components such as carbon monoxide, HCN, ammonia, phenol, nitrosamines and benzopyrene in cigarette mainstream smoke have attracted much attention. Therefore, it is a problem that the tobacco industry must solve to reduce harmful components in smoke, reduce the harm of smoking, and improve the quality and safety of cigarette products. High-quality and safe low-risk cigarettes have become the development trend of international cigarettes. As a newly developed material, carbon hollow sphere materials have many special physical and chemical properties and their wide application prospects due to their special structure. The material has the following characteristics: low density, high porosity, large specific surface and can allow liquid or gas to pass selectively, and has excellent adsorption and catalytic properties, so carbon hollow sphere materials are widely used in various functions and Structural materials. At present, the preparation of carbon hollow materials often requires higher temperatures, multi-step operation or protection of inert gases. These factors are not conducive to the mass production of carbon hollow materials, and the cost rises and cannot be applied in the industrial field. Therefore, the design of a simple synthetic route to prepare high-yield carbon hollow materials is the basis for its widespread application. In addition, the current research on the application of carbon hollow materials mainly focuses on its influence on the catalytic performance of the catalyst carrier, and the high specific surface area of carbon hollow materials and excellent adsorption properties to adsorb harmful gases in tobacco. The monk is a minority.

Summary of the invention

 SUMMARY OF THE INVENTION The object of the present invention is to provide a carbon hollow sphere material which can effectively reduce the harmful component ammonia in the flue gas to reduce the health hazard of smoking.

 To achieve the above object, the present invention adopts the following technical solutions:

 A carbon hollow sphere material obtained by the following method:

Using a polyhydroxy organic compound as a carbon source, NaN ₃ is added as a catalyst to the autoclave in a certain ratio. After sealing, the autoclave is placed in a high temperature furnace, and the temperature is raised from room temperature to 400 to 420 ° C in 40 minutes. And maintaining the temperature for 350 to 450 minutes, then the autoclave was naturally cooled to room temperature, and the product was collected. The collected product was washed successively with ethanol, dilute hydrochloric acid and water, filtered, and dried to obtain a carbon hollow sphere material.

 The above carbon source is liquid or solid, and the amount of the liquid carbon source used is generally 2 to 8 ml per gram of the catalyst, and the amount of the solid carbon source used is generally 0.5 4 g per gram of the catalyst.

 The polyhydroxy organic compound is glycerol, glucose or polyethylene glycol.

 The main composition of the obtained carbon hollow sphere material is carbon hollow sphere, and the diameter of the carbon hollow sphere is mainly distributed in the range of 100~300

 1

Confirmation The thickness of the carbon hollow sphere shell is about 20 nm. The carbon hollow sphere material has a low degree of graphitization. The thermogravimetric analysis shows that the thermal stability of the material is good and can exist stably before air at 500 °C.

 A cigarette comprising a carbon hollow sphere material as a filter layer in a filter rod. The cigarette divides the mouth stick into two sections, and a carbon hollow sphere material is disposed between the two nozzles as a filter layer.

 0.005 g of carbon hollow sphere material is used for each cigarette.

 The beneficial effects of the invention are as follows: The prepared hollow sphere has good stability, small particle size, large specific surface area, simple process and large quantity production. The use of carbon hollow sphere material as an additive to cigarette rods reduces the harmful components of ammonia in the flue gas, providing a new way to reduce harmful components in cigarette smoke to reduce the health risks of smoking.

DRAWINGS

 Figure 1 is an electron micrograph of a carbon hollow sphere material of the present invention;

 Figure 2 is an X-ray powder diffraction pattern of the carbon hollow sphere material of the present invention;

 Figure 3 is a thermograviogram of the carbon hollow sphere of the present invention in the air,

 Figure 4 is a structural view of a nozzle bar with a carbon hollow sphere material.

 Among them, 1 mouth bar, 2 carbon hollow ball material layer.

detailed description

 The invention will be further described below in conjunction with the drawings and embodiments.

 Example 1

Using glycerol as a carbon source and NaN ₃ as a catalyst, 10-15 ml of glycerol and 2 to 5' g of NaN ₃ were added to a 20 ml stainless steel autoclave. After sealing, the autoclave was placed in a high temperature furnace for 40 minutes. The internal temperature was raised from room temperature to 400 ° C and maintained at this temperature for 380 minutes. Then, the autoclave was naturally cooled to room temperature, and the product was collected. The collected product was washed successively with ethanol, dilute hydrochloric acid and water, and then suction filtered and dried to obtain a carbon hollow sphere material.

 Example 2

Using glucose as a carbon source and NaN ₃ as a catalyst, 3-8 g of glucose and 2 to 5 g of NaN ₃ were added to a 20 ml stainless steel autoclave. After sealing, the autoclave was placed in a high temperature furnace and the temperature was set in 40 minutes. It was raised from room temperature to 420 ° C and maintained at this temperature for 400 minutes. Then, the autoclave was naturally cooled to room temperature, and the product was collected. The collected product was washed successively with ethanol, dilute hydrochloric acid and water, and then suction filtered and dried to obtain a carbon hollow sphere material.

 Example 3

Using polyethylene glycol (molecular weight 200-20,000) as a carbon source, NaN ₃ as a catalyst, adding 10~15ml polyethylene glycol (molecular weight 200-20,000) and 2~5g NaN ₃ to 20ml stainless steel autoclave After sealing, the autoclave was placed in a high temperature furnace, the temperature was raised from room temperature to 420 ° C in 40 minutes, and maintained at this temperature for 430 minutes. Then autoclave naturally After cooling to room temperature, the product was collected, and the collected product was washed successively with ethanol, dilute hydrochloric acid and water, and then suction filtered and dried to obtain a carbon hollow sphere material.

 Example 4

 Performance test of the carbon hollow sphere material prepared above:

 Thermogravimetric analysis of carbon hollow sphere materials

 In air, the weight loss of the product ranges from 500 to 760 ° C, which indicates that the product has good thermal stability and can be stably present in air at 500 ° C.

 Application of carbon hollow sphere material: The nozzle stick is divided into two sections, and a carbon hollow sphere material is arranged between the two nozzles as a filter layer.

 Carbon hollow sphere material conforms to nozzle preparation

 0.002 g, 0.005 g and 0.010 g of carbon hollow sphere materials were accurately weighed and compounded into the filter of the finished cigarette to prepare a sample cigarette of a "sandwich" composite filter.

 Analysis and Detection of Tar and Ammonia in Cigarette Smoke

 Cigarette flue gas tar content is determined according to the ISO-4387 standard method. Determination of ammonia in the flue gas: 44mm Cambridge filter and a 20ml 0.01MHC1 gas absorption bottle (connected between the trap and the suction syringe) collects 4 cigarette smokes sucked by the linear smoking machine, The filter for collecting the smoke climate was placed in a 100 ml Erlenmeyer flask, and 20 ml of O.OIMHCI was added to shake extraction for 30 min, and then 5 ml of the extract and 5 ml of the absorption solution were each taken in a 25 ml volumetric flask to make a volume. After the sample was filtered through a 45 μm membrane, the sample was injected and the ammonia in the flue gas was quantitatively analyzed by ion chromatography.

 Effect of adding different amounts of carbon hollow sphere materials on ammonia reduction in flue gas

 Accurately weighed 0.002g, 0.005g, 0.010g and 0.015g carbon hollow sphere materials to make a sample cigarette of the "sandwich" composite filter. The tar and ammonia content of the sample was measured in Table 1. As the amount of carbon hollow sphere material increases, the content of tar and ammonia in the flue gas decreases in turn. The effect of carbon hollow sphere material on ammonia reduction in flue gas is very obvious, but after the addition of carbon hollow sphere material exceeds 0.005 g The decrease in tar and ammonia content in the flue gas is slowed down. Adding more carbon hollow sphere material will cause the suction resistance of the cigarette to become larger and the smoking odor of the cigarette to be significantly affected, which will affect the suction of the cigarette. The comprehensive consideration is: Adding 0.005 g of carbon hollow sphere material per cigarette It is best for reducing the ammonia and tar content of flue gas.

 Table 1 : Adding different amounts of carbon hollow sphere material to tar and ammonia content in each cigarette smoke

0.005克碳空心材料复合嘴棒样品 7.9 3.78

0.005 g carbon hollow material composite nozzle sample 7.9 3.78

0.010 g carbon hollow material composite nozzle sample 3.41 1.72 The new carbon hollow sphere material is used as an additive for cigarette rods to reduce the tar and ammonia content in the flue gas. It is found that the new carbon hollow material has a larger specific surface area and more High surface activity, stronger adsorption activity, 'It is the best to reduce tar and ammonia in flue gas, reduce the ammonia content of harmful components in flue gas to at least 60%, and because carbon material is non-toxic Harmful materials, therefore, the addition of carbon hollow sphere material to the cigarette composite nozzle to reduce the content of harmful components of ammonia in the flue gas has a great application prospect.

Claims

WO 2012/034261 Claim PCT/CN2010/002089 A carbon hollow sphere material characterized in that it is obtained by the following method: Using a polyhydroxy organic compound as a carbon source, NaN ₃ is added as a catalyst to the autoclave in a certain ratio. After sealing, the autoclave is placed in a high temperature furnace, and the temperature is raised from room temperature to 400 to 420 ° C in 40 minutes. And maintain at this temperature After 350-450 minutes, the autoclave is naturally cooled to room temperature, and the product is collected. The collected product is washed successively with ethanol, dilute hydrochloric acid and water, filtered, and dried to obtain a carbon hollow sphere material.  2. The carbon hollow sphere material according to claim 1, wherein the carbon source is liquid or solid, and the amount of the liquid carbon source used is 2 to 8 ml per gram of the catalyst, and the amount of the solid carbon source used is per gram. The catalyst is used in an amount of 0.5 to 4 grams.  The carbon hollow sphere material according to claim 1, wherein the polyhydroxy organic compound is glycerin, glucose or polyethylene glycol. 4. A method for preparing a carbon hollow sphere material, characterized in that a polyhydroxy organic compound is used as a carbon source, NaN _{3 is} used as a catalyst, and is added to an autoclave in a certain ratio, and after sealing, the autoclave is placed in a high temperature furnace. The temperature was raised from room temperature to 400 to 420 ° C in 40 minutes, and maintained at this temperature for 350 450 minutes, then the autoclave was naturally cooled to room temperature, and the product was collected, and the collected product was passed through ethanol, dilute hydrochloric acid and water. After washing, filtering and drying to obtain a carbon hollow sphere material; wherein the carbon source is liquid or solid, the amount of the liquid carbon source used is 2-8 ml per gram of the catalyst, and the amount of the solid carbon source used is 0.5 to 4 per gram of the catalyst. Gram. .  A cigarette comprising the carbon hollow sphere material according to any one of claims 1 to 3 in a filter rod.  6. A cigarette according to claim 5, wherein the mouthpiece is divided into two sections, and the carbon hollow sphere material is served as a filter layer on the two nozzles.  7. A cigarette according to claim 5 wherein 0.005 grams of carbon hollow sphere material is used per cigarette.