CN103005712A - Grapheme type fiber cigarette filter and preparation method thereof - Google Patents

Abstract

The invention discloses a graphene fiber cigarette filter tip and a preparation method thereof. The filter tip includes a fiber carrier on which a graphene material for absorbing harmful components in smoke is arranged. The filter loads graphene-like materials on carbon fiber or cellulose acetate carrier, and adds the carrier to the filter by using the existing binary filter production method in the industry to make a composite filter, which absorbs the smoke produced by cigarettes. harmful substances in the flue gas. The filter uses the unique π adsorption characteristics of new two-dimensional nanomaterials and a very high proportion of surface active atoms, and can treat benzo[a]pyrene, volatile aldehydes and ketones cancer-promoting molecules, Efficient adsorption of phenol and HCN is environmentally friendly and has no additional toxicity. Due to the small amount and high efficiency, it reduces the harm of cigarettes to the human body while not affecting the internal sensory quality of cigarettes. At the same time, the method has simple process and low cost for large-scale production, and has broad application prospects in the field of cigarette harm reduction and tar reduction.

Description

A kind of graphene fiber cigarette filter and preparation method thereof

technical field

The invention relates to the technical field of cigarettes, in particular to a graphene fiber cigarette filter and a preparation method thereof.

Background technique

Harmful substances such as NH ₃ , CO, phenol, benzo[a]pyrene, HCN, crotonaldehyde, methylnitrosamine pyridyl butanone (NNK) are produced during the burning of cigarettes, which enter the human body with the smoke during smoking and cause harm. Cigarette filters can prevent these substances from entering the human body to a certain extent.

Initially, cigarette filters were mainly made of a single fiber material, which had low adsorption efficiency for harmful substances; later, with the development of material technology, bulk composite fibers, ion exchange fibers, fiber materials doped with metal or metal oxides, Nano-carbon sols and the like are used in different ways to make cigarette filters. As in CN101019692A, discloses a kind of filter tip that evenly blends the active carbon fiber that accounts for its certain proportion in cellulose acetate, has improved filter stick or filter tip to the adsorption of volatile and semi-volatile harmful substance in mainstream smoke Efficiency; In CN1652703A, a filter is disclosed that contains a bundle of fibers that can carry particulate matter, pellets or powder to help reduce smoke components. These methods have reduced the harmful components in the mainstream smoke of cigarettes to a certain extent, but due to the characteristics of traditional polymer materials or metal chemical materials, such as poor selectivity, low polarity, and few active conjugation sites, the detection of harmful substances is difficult. The adsorption method is mainly physical adsorption, and the adsorption efficiency of harmful components in flue gas is low.

With the development of nanotechnology, nanomaterials are gradually being applied to various fields of production and life. Nanocomposite materials have been applied to the selective adsorption of harmful components in mainstream cigarette smoke. Although they are very limited, they have achieved good results. Feng Shouai et al. (Feng Shouai et al., Research on Selective Adsorption of Harmful Components in Cigarette Mainstream Smoke by Nano-SiO ₂ , Materials Herald, 2011, 25, 44-46) reported at the end of 2011 that nano-SiO ₂ was made into a dispersion and injected into the mouthpiece. Among them, the results showed that the content of benzo[a]pyrene, phenol and crotonaldehyde in the smoke was reduced by more than 8%; Xu Yihua used nano-carbon sol to make a high-efficiency cigarette filter (patent No. 200810063747. 6), and thought the effect was very good. Although nano-carbon sols have more active sites for adsorption, they also have the disadvantages of complex components, the ratio of the number of surface atoms to the total number of atoms is not optimal, and the selectivity to adsorption components is poor.

Graphene is a brand-new two-dimensional nanomaterial composed of carbon atoms with sp ² hybrid orbitals to form a honeycomb regular hexagonal lattice. In addition to the characteristics of ordinary nanomaterials, it also has a unique p-bond conjugation Adsorption and chemical catalytic activity. After its discovery, it quickly aroused a research boom all over the world, and the discoverer also won the Nobel Prize in Physics in 2010. The root of its award is that graphene has excellent properties in many aspects such as adsorption and catalysis. Graphene oxide (Graphene oxide) is a direct derivative of graphene, and has improved properties relative to graphene, such as rich hydroxyl and carboxyl functional groups on the surface, and better water solubility than graphene. In addition, in addition to retaining the good p adsorption (including Hp effect, pp effect, p _cation -p effect, cation-p effect, anion-p effect, and non-polar gas-p effect) and catalytic properties of non-polar graphene In addition, it is also easy to form hydrogen bonds with polar groups such as hydroxyl, amino, and carboxyl, and has better adsorption properties for polar molecules. Therefore, graphene and graphene oxide have a good selective adsorption effect on conjugated molecules, bases, porphyrin, aldehyde and ketone molecules, etc. In addition, B. Huang et al. (B. Huang, Z. Li, Z. Liu, G. Zhou, S. Hao, J. Wu, B. Gu, W. Duan, J. Phys. Chem. C 2008, 112, 13443.) reported that the regular hexagonal lattice of graphene matches the molecular size of NH ₃ and can adsorb small gas molecules such as nitrogen oxides.

At present, graphene and graphene oxide have been applied in various fields, but so far, graphene and graphene oxide have not yet seen relevant patents and literature reports in the field of cigarette harm reduction and tar reduction, and have not been introduced yet. and apply. The application of the new generation of two-dimensional nanomaterials represented by graphene in the present invention for reducing harm and coke in cigarettes will definitely bring new breakthroughs in cigarette technology.

Contents of the invention

Purpose of the invention: Aiming at the deficiencies in the prior art, the purpose of the present invention is to provide a graphene-based fiber cigarette filter and its preparation method, which can efficiently and selectively absorb the harmful substances produced in the smoke when the cigarette is smoked. While affecting the internal sensory quality of cigarettes, it also reduces the harm of smoking to the human body.

Technical solution: In order to realize the above-mentioned purpose of the invention, the technical solution adopted in the present invention is as follows:

A graphene fiber cigarette filter, the filter includes a fiber carrier, and a graphene material for absorbing harmful components in the smoke is arranged on the fiber carrier; the graphene material is dispersed on the on the fiber carrier.

The fiber carrier includes carbon fiber, acetate fiber, sepiolite fiber, animal and plant fiber, molecular sieve and other organic, inorganic, polymer materials, and the preparation reaction conditions are not necessarily simple mixing, but also hydrothermal method, Solid phase synthesis, active functional group coupling and other synthesis methods.

The graphene-like material is one of graphene and graphene oxide or a mixture thereof.

The filter tip is a binary composite filter tip, and the end in contact with shredded tobacco is closely connected to a fiber carrier section loaded with graphene-like materials, the thickness of the carrier is 1-4 mm, and then connected to a common acetate fiber section.

In each cigarette, the weight of the fiber carrier loaded with graphene-like materials is 5-20 mg.

A method for preparing a graphene fiber cigarette filter, comprising the following steps:

1) Evenly disperse the graphene-based material into the solvent to prepare a 0.1-10 mg/mL graphene-based solution;

2) Pre-activate the fiber carrier to remove impurities and miscellaneous gases contained in the carrier itself, and dry it;

3) Immerse the activated fiber carrier in the graphene solution for 10-60 min, and dry it; the mass of the graphene material is 0.5-15% of the fiber carrier mass;

4) Using the conventional binary filter manufacturing method, the fiber carrier loaded with the above-mentioned graphene-like material is added to the filter to make a composite filter;

In step (1), the solvent of the graphene-based solution is ethanol, water or a mixture of the two.

In step (1), the dispersion method is ultrasonic dispersion.

In step (2), the activation treatment method is boiling water for 25 minutes.

In step (3), the immersion method is ultrasonic first, then vibration, and then standing still.

Beneficial effect: compared with the prior art, the present invention has the following characteristics:

(1) Compared with traditional bulk materials and three-dimensional nanomaterials, graphene and graphene oxide have a larger surface atomic ratio, unique p-adsorption properties, and chemical catalytic activity. By adding graphene and oxide in cigarette filters Modification of graphene can greatly improve the adsorption efficiency of harmful substances in flue gas. At the same time, graphene materials have good dispersibility in water or ethanol, and are easy to compound with carbon fiber and acetate fiber carriers, and are not easy to fall off , so neither the environment nor the human body will produce additional toxicity, and it is green and environmentally friendly.

(2) High selective adsorption efficiency can be achieved with a small dosage without affecting the intrinsic sensory quality of cigarettes. After analysis and detection, the present invention improves the filtering performance of the cigarette filter by adding graphene materials to the cigarette filter for modification, and can significantly reduce the release of harmful components in cigarette smoke, and the benzo[a ]The contents of pyrene, phenol, HCN, crotonaldehyde and NH ₃ all decreased obviously, and at the same time, they had little effect on the aroma substances in the smoke. After smoking evaluation by qualified personnel in the industry, it has been confirmed that the internal quality of cigarettes modified with graphene materials has no significant change, and the effect of adding them is significantly better than that of cigarettes modified with metal or oxide methods.

(3) The manufacturing process of the filter tip is an existing mature technology in the industry, so the process of the present invention is simple, the operation is very convenient, and the cost is low during mass production.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments.

Example 1

1) Prepare 0.2 mg/mL graphene oxide aqueous solution;

2) Boil the cellulose acetate in water for 25 minutes for activation treatment, then immerse it in an aqueous solution of graphene oxide containing 1.0% of the mass of cellulose acetate, ultrasonicate for 10 minutes (80 W), let stand for 10 minutes, and dry at 110°C;

3) Add the cellulose acetate carrier loaded with the above-mentioned graphene oxide to the mouth rod by adopting the existing binary tip making method in the industry to make a composite filter. The thickness of the cellulose acetate carrier is 2 mm, and each cigarette is loaded with oxidation Graphene acetate weighs 10 mg.

4) The composite filter is made into cigarettes, and the harmful components in the mainstream smoke are detected by national standards. The analysis results are shown in Table 1.

Example 2

1) Prepare 0.5 mg/mL graphene oxide aqueous solution;

2) Boil the cellulose acetate in water for 25 min for activation treatment, then immerse it in an aqueous solution of graphene oxide containing 2.5% of the mass of cellulose acetate, ultrasonicate for 10 min (80 W), shake for 20 min (160 W), and stand for 10 min. min, dry at 110°C;

3) Add the above-mentioned graphene oxide-loaded cellulose acetate carrier to the mouth rod by using the industry's existing binary nozzle rod production method to make a composite filter. The thickness of the acetate fiber carrier is 1.5 mm, and each cigarette is loaded with oxidized The acetate weight of graphene is 8 mg.

4) The composite filter is made into cigarettes, and the harmful components in the mainstream smoke are detected by national standards. The analysis results are shown in Table 1.

Example 3

1) Prepare 0.2 mg/mL graphene ethanol solution;

2) Boil the cellulose acetate in water for 25 minutes for activation treatment, then immerse it in a graphene ethanol solution containing 1.0% of the mass of cellulose acetate, ultrasonicate for 20 minutes (80 W), shake for 20 minutes (160 W), and stand for 10 minutes. min, dry at 110°C;

3) Add the cellulose acetate carrier loaded with the above graphene to the mouth rod by using the industry’s existing binary mouth rod production method to make a composite filter. The thickness of the acetate fiber carrier is 2 mm, and graphene is loaded in each cigarette The weight of cellulose acetate is 10 mg.

4) The composite filter is made into cigarettes, and the harmful components in the mainstream smoke are detected by national standards. The analysis results are shown in Table 1.

Example 4

1) Prepare 0.2 mg/mL graphene oxide aqueous solution;

2) Boil the carbon fiber in water for 25 minutes for activation treatment, and then immerse it in an aqueous solution of graphene oxide containing 1.0% of the carbon fiber mass, sonicate for 10 minutes (80 W), shake for 20 minutes (160 W), and stand for 10 minutes. min, dry at 110°C;

3) The carbon fiber carrier loaded with the above graphene oxide is added to the mouth rod by using the existing binary nozzle rod production method in the industry to make a composite filter. The thickness of the carbon fiber carrier is 2 mm, and each cigarette carries oxidation The carbon fiber weight of graphene is 10 mg.

4) The composite filter is made into cigarettes, and the harmful components in the mainstream smoke are detected by national standards. The analysis results are shown in Table 1.

Example 5

1) Prepare 0.4 mg/mL graphene oxide aqueous solution and 0.4 mg/mL graphene ethanol solution, and mix equal volumes to obtain a mixed solution of graphene oxide and graphene;

2) Boil the carbon fiber in water for 25 min for activation treatment, and then immerse it in a mixed graphene solution containing 2.0% carbon fiber mass, ultrasonic for 20 min (80 W), shake for 20 min (160 W), and stand for 10 min. min, dry at 110°C;

3) Add the above-mentioned graphene and graphene oxide-loaded activated carbon fiber carrier to the mouth rod by adopting the industry's existing binary nozzle rod production method to make a composite filter. The thickness of the carbon fiber carrier is 1.5 mm. Each cigarette The carbon fibers loaded with graphene and graphene oxide weighed 8 mg.

4) The composite filter is made into cigarettes, and the harmful components in the mainstream smoke are detected by national standards. The analysis results are shown in Table 1.

Example 6

National standards were used to detect harmful components in mainstream smoke in cigarettes made from the composite filters of Examples 1-5, and the results are shown in Table 1.

Table 1 Results of reducing the release of harmful components in cigarette smoke

It can be seen from the data in the table that after composite modification of graphene and graphene oxide, the adsorption efficiency of major harmful substances, especially conjugated and polar small molecules, is significantly improved. These conjugated polar small molecules are recognized as harmful substances, for example, they play the role of "carcinogenesis agent" in cancer, and some people also believe that they are direct carcinogens.

The above examples all show that cigarette filters modified based on graphene and graphene oxide can effectively reduce harmful substances in cigarette smoke. The above-mentioned embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. All the implementation manners cannot be exhaustively listed here. All obvious changes or variations derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims (10)

1. Graphene fiber cigarette filter, it is characterized in that: described filter tip comprises fiber carrier, is provided with Graphene class material for absorption flue gas harmful constituent at described fiber carrier; Described Graphene class dispersion of materials is on described fiber carrier.

2. Graphene fiber cigarette filter according to claim 1, it is characterized in that: described fiber carrier comprises charcoal fiber, acetate fiber, sepiolite fibre, animal and plant fiber and molecular sieve.

3. Graphene fiber cigarette filter according to claim 1, it is characterized in that: described Graphene class material is a kind of or its mixing in Graphene and the graphene oxide.

4. Graphene fiber cigarette filter according to claim 1, it is characterized in that: described filter tip is binary combined filter tip, contact pipe tobacco end is close to the fiber carrier section that Graphene class material in load, and the thickness of carrier is 1 ~ 4 mm, then connects common acetate fiber section.

5. Graphene fiber cigarette filter according to claim 1, it is characterized in that: in described every cigarette, the fiber carrier weight of load Graphene class material is 5 ~ 20 mg.

6. a method for preparing Graphene fiber cigarette filter claimed in claim 1 is characterized in that, may further comprise the steps:

1) Graphene class material is evenly spread in the solvent, be made into the Graphene class solution of 0.1 ~ 10 mg/mL;

2) fiber carrier is carried out pre-activation process, remove impurity, assorted gas that carrier itself contains, oven dry;

3) will activate good fiber carrier and be immersed into 10 ~ 60 min in the Graphene class solution, oven dry; The quality of Graphene class material is 0.5 ~ 15% of fiber carrier quality;

4) adopt conventional dual filter preparation method, with load the fiber carrier of above-mentioned Graphene class material add in the filter tip, make composite filter tip.

7. the method for preparing Graphene fiber cigarette filter according to claim 6 is characterized in that, in the step (1), the solvent of described Graphene class solution is ethanol, water or the mixed liquor of the two.

8. the method for preparing Graphene fiber cigarette filter according to claim 6 is characterized in that, in the step (1), the mode of described dispersion is ultrasonic dispersion.

9. the method for preparing Graphene fiber cigarette filter according to claim 6 is characterized in that, in the step (2), described activation process mode is that boiling water boils 25 min.

10. the method for preparing Graphene fiber cigarette filter according to claim 6 is characterized in that, in the step (3), the submergence mode is first ultrasonic, and rear concussion is left standstill again.