CN112971205A - Application of graphene adsorption material in reducing harmful components in cigarette smoke - Google Patents
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- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 77
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 17
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Classifications
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- 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
- A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
-
- 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
- A24D3/02—Manufacture of tobacco smoke filters
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an application of a graphene adsorption material in reducing harmful components in cigarette smoke, wherein the graphene adsorption material is prepared by activating graphene oxide with KOH and reducing the graphene oxide with hydrazine hydrate as a reducing agent, and the graphene adsorption material is added into a cigarette filter to achieve the purpose of reducing the harmful components in the cigarette; the graphene adsorption material has a good adsorption effect on benzo [ a ] pyrene, hydrogen cyanide, ammonia, crotonaldehyde, phenol and CO in smoke, is simple in preparation method and mild in reaction conditions, and is large in specific surface area, stable in regular hexagonal lattice structure and easy to form acid-base conjugate interaction with a phenol compound. In addition, chemical functional groups such as carboxyl and hydroxyl on the surface of the graphene flue gas adsorption material prepared by the method can form hydrogen bonds with phenolic compounds. The additive for the cigarette filter tip can effectively reduce harmful components in smoke and has obvious tar and harm reducing effects.
Description
Technical Field
The invention relates to application of a graphene adsorption material in reducing harmful components in cigarette smoke, and belongs to the technical field of cigarettes.
Background
Cigarette smoke is an extremely complex mixture of ingredients produced by the processes of high-temperature combustion, pyrolysis, distillation and the like of tobacco products during smoking. The tar and harm reduction is always the focus and hot spot of the international tobacco community.
At present, the world admittedly has greater influence on human health by 6 main harmful substances, namely benzo [ a ] pyrene, hydrogen cyanide, ammonia, crotonaldehyde, phenol and CO. Hydrogen cyanide is a fibrous toxin, which affects respiratory cells of the human body and eventually causes death due to asphyxiation of the cells when a certain amount of hydrogen cyanide is taken in by the human body; phenol is a common bactericide and can be absorbed by respiratory tract, skin and digestive tract, low concentration phenol can denature protein, high concentration phenol can precipitate protein, has strong corrosive effect on skin and mucosa, and can inhibit damage of central nervous system to liver and kidney; ammonia gas can cause hepatic steatosis, renal interstitial inflammation and myocardial damage, low-concentration ammonia has stimulation effect on mucous membrane, and high-concentration ammonia can cause tissue lytic necrosis (i.e. saponification effect) such as tissue protein denaturation and adipose tissue saponification. Related reports show that the porous material is independently applied to the cigarette filter, has poor effect of removing harmful ingredients in cigarette smoke and low selectivity.
In the prior art, researches on removing harmful ingredients in cigarette smoke are more, mainly on two aspects, namely on the aspect of cigarette processing technology, for example, in patent 201110241462.9, SiO is added into a cigarette filter stick2The reduction rates of crotonaldehyde and phenol were 10.3% and 20.1%, respectively; the other is to prepare the cigarette additive, which is added into the filter to achieve the purpose of adsorption, for example, in patent 200710034453.6, the reduction rate of phenol can only reach 31 percent by adding modified activated carbon fiber into the cigarette filter; sunyufeng, etc. uses MMM as additive of cigarette filter tip and p-benzo [ a ]]The reduction rates of pyrene, crotonaldehyde and phenol were: 26.25%, 8.15%, 43.40%, it is clear that the reduction rate is to be improved. In addition, in patent CN201410134481, the adsorption capacity for ammonia gas can reach more than 30%, but the amount of the material added in the patent is more than 40mg, and too much amount of the material added in the filter tip affects the suction resistance and is not beneficial to suction.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a new application of a graphene adsorption material, namely the application of the graphene adsorption material in reducing harmful components in cigarette smoke, the graphene adsorption material is prepared by activating graphene oxide with KOH and then reducing the graphene oxide with hydrazine hydrate as a reducing agent on the premise of not changing cigarette formula components, and the graphene adsorption material is used as an adsorbent and is added to a cigarette filter 2/3, the graphene adsorption material has large specific surface area and adjustable pore diameter, has a stable regular hexagonal lattice structure, and is easy to form acid-base conjugate interaction with a phenol compound, so that the graphene adsorption material has obvious adsorption on the harmful components of benzo [ a ] pyrene, hydrogen cyanide, ammonia, crotonaldehyde, phenol and CO in the cigarette smoke, the benzo [ a ] pyrene reduction rate can reach more than 20%, the hydrogen cyanide reduction rate can reach more than 58%, and the ammonia reduction rate can reach more than 37%, The crotonaldehyde reduction rate can reach more than 37%, the phenol reduction rate can reach more than 50%, and the CO reduction rate can reach more than 11%.
The preparation method of the graphene adsorption material comprises the following steps:
(1) adding flake graphite into a mixed solution of hydrochloric acid and hydrofluoric acid, stirring and reacting for 2-5 h, carrying out solid-liquid separation, washing and drying solids to obtain pretreated graphite, oxidizing the pretreated graphite at 50-80 ℃ by using concentrated sulfuric acid containing phosphorus pentoxide and potassium persulfate, carrying out dehydration treatment, carrying out solid-liquid separation, washing and drying the solids to obtain the preoxidized graphite, sequentially adding the preoxidized graphite, sodium nitrate and potassium permanganate into the concentrated sulfuric acid, then placing the mixture in a water bath at 0-35 ℃ for stirring and reacting for 4-10 h, carrying out solid-liquid separation, washing the solids to pH 7 by using hydrochloric acid and deionized water in sequence, drying, adding water into the solids, and carrying out ultrasonic dispersion to obtain a graphene oxide suspension;
the hydrochloric acid-hydrofluoric acid mixed solution is prepared by mixing hydrochloric acid and hydrofluoric acid according to the volume ratio (0.5-1) to 1;
the concentration of the phosphorus pentoxide in concentrated sulfuric acid is 75-150 g/L, the concentration of potassium persulfate in concentrated sulfuric acid is 75-150 g/L, the mass ratio of the concentrated sulfuric acid containing the phosphorus pentoxide and the potassium persulfate to the pretreated graphite is (0.5-1): 0.5-1, and the concentrated sulfuric acid is a conventional commercial product;
the mass ratio of the concentrated sulfuric acid to the pre-oxidized graphite is (0.5-1) to (0.5-1), and the mass ratio of the pre-oxidized graphite to the sodium nitrate to the potassium permanganate is (1-1.5) to (1-6);
(2) adding KOH into the graphene oxide suspension, and stirring in a water bath at the temperature of 25-40 ℃ for 1-2.5 h;
the mass ratio of the KOH to the graphene oxide is 1 (2-5);
(3) adding ammonia water into the suspension after stirring in the step (2) to adjust the pH value to 2-6, then adding hydrazine hydrate, stirring and reacting for 4-8 h under the condition of oil bath at the temperature of 55-95 ℃, after the reaction is finished, carrying out solid-liquid separation, washing the solid to be neutral by using deionized water and absolute ethyl alcohol in sequence, and carrying out vacuum drying to obtain the graphene adsorbing material; the mass ratio of the graphene oxide to the hydrazine hydrate is (0.5-1) to 4.
The graphene adsorption material is used as a cigarette additive, the graphene smoke adsorption material is added to 2/3 positions of cigarette filters, harmful ingredients in cigarette smoke can be reduced, and the addition amount of the graphene adsorption material in each cigarette filter is 5-20 mg.
The harmful components in the cigarette smoke comprise benzo [ a ] pyrene, hydrogen cyanide, ammonia, crotonaldehyde, phenol and CO.
The technical scheme of the invention has the following advantages:
(1) according to the invention, on the premise of not changing cigarette formula components, the graphene adsorption material is added to the cigarette filter 2/3 as an adsorbent. The graphene adsorption material is large in specific surface area, adjustable in pore size, stable in regular hexagonal lattice structure and easy to form acid-base conjugate interaction with a phenol compound, so that the graphene adsorption material has obvious adsorption on harmful components of benzo [ a ] pyrene, hydrogen cyanide, ammonia, crotonaldehyde, phenol and CO in cigarette smoke, the benzo [ a ] pyrene reduction rate can reach more than 23%, the hydrogen cyanide reduction rate can reach more than 58%, the ammonia reduction rate can reach more than 37%, the crotonaldehyde reduction rate can reach more than 37%, the phenol reduction rate can reach more than 50%, and the CO reduction rate can reach more than 11%;
(2) according to the invention, the graphene flue gas adsorption material is prepared by a KOH activation method, the preparation process is simple and easy to operate, the pollution of waste liquid generated in the graphene preparation process to the environment is effectively avoided, and the reproducibility is good;
(3) chemical functional groups such as carboxyl and hydroxyl on the surface of the graphene flue gas adsorption material prepared by the invention can form hydrogen bonds with phenolic compounds;
(4) after the graphene smoke material prepared by the invention is used for preparing a composite filter tip in a cigarette filter tip, the graphene smoke material has a good adsorption effect on harmful components in cigarette smoke, and the material is determined not to migrate along with the smoke through material migration detection, so that the graphene smoke material has good safety.
Drawings
FIG. 1 shows N in a graphene adsorbent2Adsorption-desorption curve (a) and pore size distribution (b).
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited thereto.
Example 1: the preparation method of the graphene adsorption material comprises the following steps:
(1) adding the crystalline flake graphite into a single-neck flask filled with a hydrochloric acid-hydrofluoric acid mixture (volume ratio of 0.5: 1), stirring for reaction for 3 hours, carrying out solid-liquid separation, washing and drying solids to obtain pretreated graphite, oxidizing and dehydrating the pretreated graphite by concentrated sulfuric acid containing phosphorus pentoxide (75 g/L) and potassium persulfate (75 g/L), stirring for 6 hours at 50 ℃, carrying out solid-liquid separation, washing and drying solids to obtain pre-oxidized graphite, wherein the mass ratio of the concentrated sulfuric acid containing the phosphorus pentoxide and the potassium persulfate to the pretreated graphite is 1: 0.75; adding pre-oxidized graphite, sodium nitrate and potassium permanganate into concentrated sulfuric acid in sequence, then placing the mixture into a water bath at 0 ℃ to be stirred and react for 10 hours, wherein the mass ratio of the concentrated sulfuric acid to the pre-oxidized graphite is 1:0.75, the mass ratio of the pre-oxidized graphite to the sodium nitrate to the potassium permanganate is 1:1:4, carrying out solid-liquid separation, washing the solid with hydrochloric acid and deionized water in sequence until the pH value is 7, carrying out freeze drying, adding water into the solid, and carrying out ultrasonic dispersion to obtain a graphene oxide suspension;
(2) adding KOH into the graphene oxide suspension, and then placing the graphene oxide suspension in a water bath at 25 ℃ to stir for 1.5h, wherein the mass ratio of KOH to graphene oxide is 1: 2;
(3) adding ammonia water into the stirred solution to adjust the pH value of the system to be 3, adding hydrazine hydrate into the suspension, stirring and reacting for 5 hours under the condition of oil bath at 95 ℃, carrying out solid-liquid separation after the reaction is finished, washing the solid to be neutral by deionized water and absolute ethyl alcohol in sequence, and carrying out vacuum drying for 8 hours at 60 ℃ to obtain the graphene flue gas adsorption material; wherein the mass ratio of the graphene oxide to the hydrazine hydrate is 0.5: 4;
n was applied to the adsorbent of this example2The adsorption-desorption test is carried out, the BET theory is adopted for the specific surface area, the BJH model is adopted for calculating the pore size distribution, and the specific surface area of the adsorption material in the embodiment is 604.9m2Per g, pore volume of 0.852cm3(ii)/g, average pore diameter 6.02 nm;
grinding and sieving the graphene adsorbing material prepared by the embodiment to 40-60 meshes, uniformly and flatly adding the adsorbing material to 2/3 parts of a cigarette filter, wherein the adding amount is 20mg per cigarette, and finally preparing a cigarette product. Blank cigarettes without added graphene adsorption materials are used as a control, 6 cigarettes are tested in each sample, 2 groups of parallel samples are arranged, and smoke components are collected by a trap with a built-in Cambridge filter disc. Before the experiment, all samples and Cambridge filter discs are placed in a constant temperature and humidity balance box with the temperature of 20 +/-2 ℃ and the humidity of 60 +/-2% for 48 hours, and the contents of benzo [ a ] pyrene, hydrogen cyanide, ammonia, crotonaldehyde, phenol and CO in cigarette smoke passing through a filter tip are respectively measured by using a British Sirullin SM450 type linear smoking machine according to a method specified in GB/T19609-2004; compared with a blank group, the cigarette added with the graphene adsorption material has the advantages that the benzo [ a ] pyrene in the smoke of the cigarette is reduced by 32.63%, the hydrogen cyanide is reduced by 63.21%, the ammonia is reduced by 42.91%, the crotonaldehyde is reduced by 37.60%, the phenol is reduced by 53.99%, and the CO is reduced by 11.71%; meanwhile, CrAPO-5 in CN108187603A is used as an additive of the cigarette filter tip, 20mg is added under the same condition for comparison, and the comparison result is shown in Table 1;
TABLE 1 reduction of harmful substances in cigarette smoke
Example 2: the preparation method of the graphene adsorption material comprises the following steps:
(1) adding the crystalline flake graphite into a single-neck flask filled with a hydrochloric acid-hydrofluoric acid mixture (volume ratio of 1: 1), stirring for reaction for 4 hours, carrying out solid-liquid separation, washing and drying solids to obtain pretreated graphite, oxidizing and dehydrating the pretreated graphite by concentrated sulfuric acid containing phosphorus pentoxide (100 g/L) and potassium persulfate (100 g/L), stirring for 6 hours at 60 ℃, carrying out solid-liquid separation, washing and drying the solids to obtain pre-oxidized graphite, wherein the mass ratio of the concentrated sulfuric acid containing the phosphorus pentoxide and the potassium persulfate to the pretreated graphite is 1: 1; adding pre-oxidized graphite, sodium nitrate and potassium permanganate into concentrated sulfuric acid in sequence, and then placing the mixture in a water bath at 15 ℃ to stir and react for 8 hours, wherein the mass ratio of the concentrated sulfuric acid to the pre-oxidized graphite is 1:1, and the mass ratio of the pre-oxidized graphite to the sodium nitrate to the potassium permanganate is 1.25:1: 4; after the reaction is finished, carrying out solid-liquid separation, washing the solid with hydrochloric acid and deionized water in sequence until the pH value is 7, freeze-drying, adding water into the solid, and carrying out ultrasonic dispersion to obtain a graphene oxide suspension;
(2) adding KOH into the graphene oxide suspension, and then placing the graphene oxide suspension in a water bath at 30 ℃ to stir for 2.5h, wherein the mass ratio of the KOH to the graphene oxide is 1: 5;
(3) adding ammonia water into the stirred solution to adjust the pH value of the system to be 5, adding hydrazine hydrate into the suspension, stirring and reacting for 5 hours under an oil bath at 85 ℃, after the reaction is finished, carrying out solid-liquid separation, washing the solid to be neutral by using deionized water and absolute ethyl alcohol in sequence, and carrying out vacuum drying for 8 hours at 60 ℃ to obtain the graphene flue gas adsorption material; wherein the mass ratio of the graphene oxide to the hydrazine hydrate is 0.75: 4;
n was applied to the adsorbent of this example2The adsorption-desorption test is carried out, the BET theory is adopted for the specific surface area, the BJH model is adopted for calculating the pore size distribution, and the specific surface area of the adsorption material in the embodiment is 623.2m2Per g, pore volume of 0.939cm3(ii)/g, average pore diameter 6.31 nm;
grinding and sieving the graphene adsorbing material prepared by the embodiment to 40-60 meshes, uniformly and flatly adding the adsorbing material to 2/3 parts of a cigarette filter, wherein the adding amount is 5mg per cigarette, and finally preparing a cigarette product. And (3) taking blank cigarettes without the graphene smoke adsorbing material as a control, testing 6 cigarettes in each sample, setting 2 groups of parallel samples, and collecting smoke components by using a catcher with a built-in Cambridge filter disc. Before the experiment, all samples and Cambridge filter discs are placed in a constant temperature and humidity balance box with the temperature of 20 +/-2 ℃ and the humidity of 60 +/-2% for 48 hours, and the contents of benzo [ a ] pyrene, hydrogen cyanide, ammonia, crotonaldehyde, phenol and CO in cigarette smoke passing through a filter tip are respectively measured by using a British Sirullin SM450 type linear smoking machine according to a method specified in GB/T19609-2004; the cigarette added with the graphene material reduces 23.18% of benzo [ a ] pyrene, 59.09% of hydrogen cyanide, 37.40% of ammonia, 42.07% of crotonaldehyde, 51.57% of phenol and 25.90% of CO in cigarette smoke, and compared with microporous mesoporous composite materials (MMM) prepared by other researchers in the field, the cigarette added amount of 5mg in each cigarette is shown in Table 2 in the comparison result under the same condition;
TABLE 2 reduction of harmful substances in cigarette smoke
Example 3: the preparation method of the graphene flue gas adsorption material sample 3 is as follows:
(1) adding the crystalline flake graphite into a single-neck flask filled with a hydrochloric acid-hydrofluoric acid mixture (volume ratio of 0.75: 1), stirring for reaction for 5 hours, carrying out solid-liquid separation, washing and drying the solid to obtain pretreated graphite, oxidizing and dehydrating the pretreated graphite by concentrated sulfuric acid containing phosphorus pentoxide (125 g/L) and potassium persulfate (125 g/L), stirring for 6 hours at 70 ℃, carrying out solid-liquid separation, washing and drying to obtain pre-oxidized graphite, wherein the mass ratio of the concentrated sulfuric acid containing the phosphorus pentoxide and the potassium persulfate to the pretreated graphite is 0.5: 1; adding pre-oxidized graphite, sodium nitrate and potassium permanganate into concentrated sulfuric acid in sequence, and then placing the mixture in a water bath at 25 ℃ to be stirred and react for 6 hours, wherein the mass ratio of the concentrated sulfuric acid to the pre-oxidized graphite is 0.5:1, and the mass ratio of the pre-oxidized graphite to the sodium nitrate to the potassium permanganate is 1.5:1: 6; after the reaction is finished, carrying out solid-liquid separation, washing the solid with hydrochloric acid and deionized water in sequence until the pH value is 7, freeze-drying, adding water into the solid, and carrying out ultrasonic dispersion to obtain a graphene oxide suspension;
(2) adding KOH into the graphene oxide suspension, and then placing the graphene oxide suspension in a water bath at 40 ℃ to stir for 1h, wherein the mass ratio of KOH to graphene oxide is 1: 3;
(3) adding ammonia water into the stirred solution to adjust the pH value of the system to be 6, adding hydrazine hydrate into the suspension, stirring and reacting for 5 hours under a 65 ℃ oil bath, performing solid-liquid separation after the reaction is finished, washing the solid to be neutral by deionized water and absolute ethyl alcohol in sequence, and performing vacuum drying for 8 hours at 60 ℃ to obtain the graphene flue gas adsorption material; wherein the mass ratio of the graphene oxide to the hydrazine hydrate is 1: 4;
n was applied to the adsorbent of this example2The adsorption-desorption test is carried out, the BET theory is adopted for the specific surface area, the BJH model is adopted for calculating the pore size distribution, and the specific surface area of the adsorption material in the embodiment is 603.5m2Per g, pore volume of 0.855cm3(ii)/g, average pore diameter 5.94 nm;
grinding and sieving the graphene adsorption material sample 3 prepared in the embodiment to 40-60 meshes, uniformly and flatly adding the adsorption material to 2/3 cigarette filters, wherein the addition amount is 10mg per cigarette, and finally preparing the cigarette product. Blank cigarettes without added graphene adsorption materials are used as a control, 6 cigarettes are tested in each sample, 2 groups of parallel samples are arranged, and smoke components are collected by a trap with a built-in Cambridge filter disc. Before the experiment, all samples and Cambridge filter discs are placed in a constant temperature and humidity balance box with the temperature of 20 +/-2 ℃ and the humidity of 60 +/-2% for 48 hours, the contents of benzo [ a ] pyrene, hydrogen cyanide, ammonia, crotonaldehyde, phenol and CO in cigarette smoke passing through a filter tip are respectively measured by a British Sirullin SM450 type linear smoking machine according to the method specified in GB/T19609-2004, and the cigarette added with the graphene material can reduce 37.67% of benzo [ a ] pyrene, 58.91% of hydrogen cyanide, 48.69% of ammonia, 43.72% of crotonaldehyde, 76.58% of phenol and 20.68% of CO in the cigarette smoke. In patent CN107416857B, CoAPO-11 is taken as an additive of a cigarette filter under the same conditions, and the comparison results of the reduction rate are shown in Table 3;
TABLE 3 reduction of harmful substances in cigarette smoke
Example 4: the preparation method of the graphene adsorption material comprises the following steps:
(1) adding the crystalline flake graphite into a single-neck flask filled with a hydrochloric acid-hydrofluoric acid mixture (volume ratio of 0.8: 1), stirring for reaction for 2 hours, carrying out solid-liquid separation, washing and drying to obtain pretreated graphite, oxidizing and dehydrating the pretreated graphite by concentrated sulfuric acid containing phosphorus pentoxide (150 g/L) and potassium persulfate (150 g/L), stirring for 6 hours at 80 ℃, carrying out solid-liquid separation, washing and drying the solid to obtain the preoxidized graphite, wherein the mass ratio of the concentrated sulfuric acid containing the phosphorus pentoxide and the potassium persulfate to the pretreated graphite is 1: 0.5; adding pre-oxidized graphite, sodium nitrate and potassium permanganate into concentrated sulfuric acid in sequence, and then placing the mixture in a water bath at 35 ℃ to be stirred and react for 4 hours, wherein the mass ratio of the concentrated sulfuric acid to the pre-oxidized graphite is 1:0.5, and the mass ratio of the pre-oxidized graphite to the sodium nitrate to the potassium permanganate is 1:1: 6; after the reaction is finished, carrying out solid-liquid separation, washing the solid with hydrochloric acid and deionized water in sequence until the pH value is 7, freeze-drying, adding water into the solid, and carrying out ultrasonic dispersion to obtain a graphene oxide suspension;
(2) adding KOH into the graphene oxide suspension, and then placing the graphene oxide suspension into a water bath at 35 ℃ to stir for 2 hours, wherein the mass ratio of KOH to graphene oxide is 1: 3;
(3) adding ammonia water into the stirred solution to adjust the pH value of the system to be 5, adding hydrazine hydrate into the suspension, stirring and reacting for 8 hours under 55 ℃ oil bath, carrying out solid-liquid separation after the reaction is finished, washing the solid to be neutral by deionized water and absolute ethyl alcohol in sequence, and carrying out vacuum drying for 8 hours at 60 ℃ to obtain the graphene flue gas adsorption material; wherein the mass ratio of the graphene oxide to the hydrazine hydrate is 0.8: 4;
n was applied to the adsorbent of this example2The adsorption-desorption test is carried out, the BET theory is adopted for the specific surface area, the BJH model is adopted for calculating the pore size distribution, and the specific surface area of the adsorption material in the embodiment is 655.1m2Per g, pore volume of 1.069cm3In terms of/g, the mean pore diameter is 6.26 nm. Obtained N2The adsorption-desorption curve and the pore diameter distribution diagram are shown in figure 1, and as can be seen from figure 1, the adsorption-desorption curve belongs to a type IV isotherm, the adsorption-desorption hysteresis phenomenon is obvious, and the hysteresis loop belongs to H3The type shows that the mesoporous pore canal is a slit-shaped pore, and the structure is favorable for cutting part of harmful ingredients in smoke gasThe catalyst is left in the pore canal, and has better effect on reducing harmful substances;
grinding and sieving the graphene adsorption material prepared by the embodiment to 40-60 meshes, uniformly and flatly adding the adsorption material to 2/3 cigarette filters, wherein the addition amount is 15mg per cigarette, finally preparing a cigarette product, testing 6 cigarettes in each sample by taking blank cigarettes without the graphene smoke adsorption material as a control, setting 2 groups of parallel samples, and collecting smoke components by using a catcher with a built-in Cambridge filter. Before the experiment, all samples and Cambridge filter discs are placed in a constant temperature and humidity balance box with the temperature of 20 +/-2 ℃ and the humidity of 60 +/-2% for 48 hours, the contents of benzo [ a ] pyrene, hydrogen cyanide, ammonia, crotonaldehyde, phenol and CO in cigarette smoke passing through a filter tip are respectively measured by using a British Silrin SM450 type linear smoking machine according to a method specified in GB/T19609-2004, and the cigarette added with the graphene material can reduce 35.57% of benzo [ a ] pyrene, 76.79% of hydrogen cyanide, 56.43% of ammonia, 46.59% of crotonaldehyde, 83.69% of phenol and 38.12% of the cigarette smoke. Under the same conditions, compared with mesoporous titanium phosphate materials prepared by other researchers in the field, the comparative results are shown in table 4;
TABLE 4 reduction rate of harmful substances in cigarette smoke
Claims (9)
1. The application of the graphene adsorption material in reducing harmful components in cigarette smoke is characterized in that: the graphene adsorption material is prepared by activating graphene oxide with KOH and reducing the graphene oxide with hydrazine hydrate as a reducing agent, and is added into a cigarette filter to achieve the purpose of reducing harmful components in cigarettes.
2. The application of claim 1, wherein the graphene adsorption material is prepared by the following steps:
(1) adding flake graphite into a mixed solution of hydrochloric acid and hydrofluoric acid, stirring and reacting for 2-5 h, carrying out solid-liquid separation, washing and drying solids to obtain pretreated graphite, oxidizing the pretreated graphite at 50-80 ℃ by using concentrated sulfuric acid containing phosphorus pentoxide and potassium persulfate, carrying out dehydration treatment, carrying out solid-liquid separation, washing and drying the solids to obtain the preoxidized graphite, sequentially adding the preoxidized graphite, sodium nitrate and potassium permanganate into the concentrated sulfuric acid, then placing the mixture in a water bath at 0-35 ℃ for stirring and reacting for 4-10 h, carrying out solid-liquid separation, washing the solids to pH 7 by using hydrochloric acid and deionized water in sequence, drying, adding water into the solids, and carrying out ultrasonic dispersion to obtain a graphene oxide suspension;
(2) adding KOH into the graphene oxide suspension, and stirring in a water bath at the temperature of 25-40 ℃ for 1-2.5 h;
(3) and (3) adding ammonia water into the suspension after stirring in the step (2) to adjust the pH value to 2-6, then adding hydrazine hydrate, stirring and reacting for 4-8 h under an oil bath at 55-95 ℃, after the reaction is finished, carrying out solid-liquid separation, washing the solid to be neutral by using deionized water and absolute ethyl alcohol in sequence, and carrying out vacuum drying to obtain the graphene adsorbing material.
3. Use according to claim 2, characterized in that: the hydrochloric acid-hydrofluoric acid mixed solution is prepared by mixing hydrochloric acid and hydrofluoric acid according to the volume ratio (0.5-1) to 1.
4. Use according to claim 2, characterized in that: the concentration of the phosphorus pentoxide in the concentrated sulfuric acid is 75-150 g/L, the concentration of the potassium persulfate in the concentrated sulfuric acid is 75-150 g/L, and the mass ratio of the concentrated sulfuric acid containing the phosphorus pentoxide and the potassium persulfate to the pretreated graphite is (0.5-1): 0.5-1.
5. Use according to claim 2, characterized in that: the mass ratio of concentrated sulfuric acid to pre-oxidized graphite is (0.5-1) to (0.5-1), and the mass ratio of pre-oxidized graphite to sodium nitrate to potassium permanganate is (1-1.5) to (1-6).
6. Use according to claim 2, characterized in that: the mass ratio of KOH to graphene oxide is 1 (2-5).
7. Use according to claim 2, characterized in that: the mass ratio of the graphene oxide to the hydrazine hydrate is (0.5-1) to 4.
8. Use according to claim 1, characterized in that: the addition amount of the graphene adsorption material in the cigarette filter is 5-20 mg/cigarette.
9. Use according to claim 1, characterized in that: harmful components in cigarette include benzo [ a ] pyrene, hydrogen cyanide, ammonia, crotonaldehyde, phenol and CO.
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