CN112107027B - Functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke and application thereof - Google Patents
Functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke and application thereof Download PDFInfo
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- CN112107027B CN112107027B CN202011115455.XA CN202011115455A CN112107027B CN 112107027 B CN112107027 B CN 112107027B CN 202011115455 A CN202011115455 A CN 202011115455A CN 112107027 B CN112107027 B CN 112107027B
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- geopolymer
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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
- A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
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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
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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
- A24D3/18—Mouthpieces for cigars or cigarettes; Manufacture thereof
Abstract
The invention belongs to the technical field of cigarette harm and tar reduction, and particularly discloses a functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke and application thereof. The functionalized polymer material has good selectivity and high adsorption rate, and can effectively reduce the release amount of hydrocyanic acid in cigarette smoke without affecting the smoking quality of cigarettes when being added into cigarette filters.
Description
Technical Field
The invention belongs to the technical field of harm and tar reduction of cigarettes, and particularly relates to a functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke and application thereof.
Background
Hydrocyanic acid (HCN) is a highly volatile A-type hypertoxic, is combined with in vivo high-iron cytochrome oxidase after being inhaled to become cyaniding high-iron cytochrome oxidase, loses the function of transferring oxygen, causes hypoxia and poisoning, and is extremely harmful to human bodies. Hydrocyanic acid is a main harmful substance in cigarette smoke, is mainly generated by cracking amino acid and related compounds at 700-1000 ℃, and has the content of about 30-300 mu g/cigarette smoke. Improving the safety of smoking cigarettes and reducing the hydrocyanic acid release amount in the cigarettes are an important direction of current tobacco research and also important guarantee for maintaining the health of smokers.
At present, hydrocyanic acid in a gas phase is difficult to treat, and the adopted methods mainly comprise a dilution method, an adsorption method and a catalytic oxidation method. Wherein, the catalytic temperature of the catalytic oxidation method is high (for example, patents CN1416950A and CN1462652A, the catalytic temperature is 250-450 ℃), and harmful gaseous products may be generated, which cannot be applied to removing hydrocyanic acid in cigarette smoke; the dilution method causes great loss of cigarette aroma amount and influences the smoking quality; the adsorption method becomes the most common method for reducing the hydrocyanic acid release amount of the mainstream smoke of the cigarettes at home and abroad due to the application convenience.
In the research of removing hydrocyanic acid in smoke by an adsorption method, active carbon is deeply researched, the active carbon has good adsorbability but poor selectivity, the cigarette smoking quality can be reduced while gas-phase components of the smoke are adsorbed, and the method has great limitation. For example: patent CN103030141A discloses a method for preparing a modified carbon material for selectively reducing the release amount of hydrocyanic acid in flue gas, which comprises soaking activated carbon in a copper sulfate solution to load copper ions on the surface of the activated carbon, and selectively adsorbing hydrocyanic acid in flue gas by using the copper ions. Therefore, there is a need to develop a novel material for effectively reducing hydrocyanic acid in cigarette smoke, and simultaneously, the smoking quality of the cigarette is not affected, and the smoking safety of the cigarette is improved.
Disclosure of Invention
One of the purposes of the invention is to provide a functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke, which has good selectivity and high adsorption rate, can effectively reduce the release amount of hydrocyanic acid in the smoke, and does not influence the smoking quality of cigarettes.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
a functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke is a geopolymer loaded with chitosan and metal ions.
The functionalized geopolymer material takes geopolymer as a main body and loads chitosan and metal ions, on one hand, CN < - > of hydrocyanic acid is strong in electronegativity and can easily form a complex with the metal ions, on the other hand, a large number of active amino groups are contained in a chitosan molecular structure and can perform acid-base neutralization reaction with the hydrocyanic acid, and the chitosan and the metal ions have synergistic effect and selectively adsorb the hydrocyanic acid in cigarette smoke; in addition, the geopolymer is of a porous structure, has a large specific surface area and can provide sufficient loading sites and adsorption areas, so that the adsorption rate is high, the adsorption speed is high, and the hydrocyanic acid release amount in the flue gas can be effectively reduced; the functionalized geopolymer material has no peculiar smell, does not influence the smoking quality of cigarettes, does not generate harmful substances in the smoking process, and has good safety.
Preferably, the metal ion is nickel ion (Ni)2+). The metal ion may be Cu2+、Zn2+、Fe3+、Co2+The metal ions may be one kind or a mixture of plural kinds, but Ni2+The functionalized polymer material is most easily loaded, and the loading effect is the best.
Preferably, the functionalized polymer material is obtained by adopting a polymer composite matrix synthesized by chitosan, sodium hydroxide, sodium silicate and nano clay, and then soaking the metal ion solution in the polymer composite matrix. The polymer composite matrix synthesized by using sodium silicate and nano clay as main geopolymer raw materials, sodium hydroxide as an alkali activator for catalytic reaction and chitosan as a structure toughening agent has high mechanical strength, good structure stability and good adsorbability on metal ions, particularly nickel ions.
Preferably, the functionalized polymer is prepared by the following steps:
s1, adding chitosan into a mixed solution of sodium hydroxide and sodium silicate, and stirring for 1.5-2.5 hours at normal temperature to obtain an alkali-activated solution, wherein the concentration of the chitosan is 5-15 g/L, and the concentration of the sodium silicate is 10-20 g/L;
s2, adding nano clay into the alkali-activated solution according to the addition amount of 15-25 g/L, reacting at 38-45 ℃ for 0.5-2.0 h, and drying the reaction product to obtain a geopolymer composite matrix;
and S3, dipping the geopolymer composite matrix into the metal ion solution, and drying to obtain the functionalized geopolymer material.
Preferably, in step S1, the concentration of sodium hydroxide in the mixed solution is 0.5 to 1.5 mol/L.
Preferably, in step S2, the nanoclay is added to the alkali-activated solution, and then is ultrasonically dispersed for 0.5 to 1 hour before reaction.
Preferably, in step S2, the drying temperature is 75-85 ℃ and the drying time is 40-60 h.
Preferably, in step S3, the metal ion concentration in the metal ion solution is 0.5 to 2mol/L, and the geopolymer composite matrix is immersed in the metal ion solution for 3 to 5 hours while stirring.
Another object of the present invention is to provide a method for using the functionalized polymer material.
The application of the functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke in cigarettes is to add the functionalized geopolymer material into cigarette filters, wherein the addition amount is 10-40 mg/cigarette.
Preferably, the functionalized polymer material is added in the middle of the filter.
The invention has the following beneficial effects:
1. the functionalized geopolymer material takes geopolymer as a main body, loads chitosan and metal ions, and selectively adsorbs hydrocyanic acid in cigarette smoke by utilizing the complexation reaction of the metal ions and hydrocyanic acid and the neutralization reaction of chitosan molecules and hydrocyanic acid; the porous structure of the polymer is combined, the loading amount is high, the adsorption rate of hydrocyanic acid is high, the adsorption speed is high, and the hydrocyanic acid release amount in the smoke can be effectively reduced (HCN can be reduced by about 30%); the functionalized geopolymer material has no peculiar smell, does not influence the smoking quality of cigarettes, does not generate harmful substances in the smoking process, and has good safety.
2. The metal ions and the chitosan of the invention are firmly loaded on the geopolymer, the stability is good, the activity is high, and the adsorption effect of hydrocyanic acid can be ensured. Specifically, the structure of the geopolymer is a 'crystal-like' structure formed by cyclic molecular chains, the cyclic molecules are combined to form a cavity (cage shape), and metal ions are divided and enclosed in the cavity, so that the geopolymer can more effectively disperse and fix the metal ions; the chitosan is not only a neutralizer of hydrocyanic acid, but also a structural toughening agent of a geopolymer, a hydrogen bond of the chitosan is connected with a geopolymer gelled substance through Van der Waals force and a coordination bond, silane hydroxyl and a low molecular polymer hydrolyzed in the geopolymerization process are condensed with a hydroxyl component in the chitosan to form a covalent bond, and the organic-inorganic flexible bonds cover and connect structural units in the geopolymer process, so that the chitosan is firmly embedded in the geopolymer while the geopolymer is toughened.
3. Compared with adsorbing materials such as activated carbon, graphene and MOF, the functionalized geopolymer material disclosed by the invention is simple in synthesis process, low in cost, high in adsorption efficiency and good in popularization and application prospects.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke is a geopolymer loaded with chitosan and nickel ions, and is prepared by the following steps:
s1, adding 1g of chitosan into 100ml of mixed solution containing 0.1mol of sodium hydroxide and 1.5g of sodium silicate, and stirring for 2 hours at normal temperature to obtain alkali-activated solution;
s2, adding 2g of nano clay into the alkali-activated solution, performing ultrasonic dispersion for 45min, then reacting for 1h at 40 ℃, and drying the reaction product for 48h at 80 ℃ to obtain a geopolymer composite matrix;
s3, soaking the geopolymer composite matrix in nickel ion solution with the concentration of 1mol/L for 4 hours, stirring the soaking process, and drying the soaked matrix to obtain the functional geopolymer material Ni2+-geopolymer/chitosan。
Example 2
A functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke is a geopolymer loaded with chitosan and nickel ions, and is prepared by the following steps:
s1, adding 0.5g of chitosan into 100ml of mixed solution containing 0.05mol of sodium hydroxide and 1.0g of sodium silicate, and stirring for 1.5h at normal temperature to obtain alkali-activated solution;
s2, adding 1.5g of nano clay into the alkali-activated solution, performing ultrasonic dispersion for 0.5h, then reacting for 2.0h at 38 ℃, and drying the reaction product for 40h at 75 ℃ to obtain a geopolymer composite matrix;
s3, soaking the geopolymer composite matrix in a nickel ion solution with the concentration of 0.5mol/L for 3 hours, stirring the soaking process, and drying the soaked matrix to obtain the functional geopolymer material Ni2+-geopolymer/chitosan。
Example 3
A functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke is a geopolymer loaded with chitosan and nickel ions, and is prepared by the following steps:
s1, adding 1.5g of chitosan into 100ml of mixed solution containing 0.15mol of sodium hydroxide and 2.0g of sodium silicate, and stirring for 2.5 hours at normal temperature to obtain alkali-activated solution;
s2, adding 2.5g of nano clay into the alkali-activated solution, performing ultrasonic dispersion for 1h, then reacting for 0.5h at 45 ℃, and drying the reaction product for 60h at 85 ℃ to obtain a geopolymer composite matrix;
s3, soaking the geopolymer composite matrix in a nickel ion solution with the concentration of 2mol/L for 5 hours, stirring the soaking process, and drying the soaked matrix to obtain the functional geopolymer material Ni2+-geopolymer/chitosan。
Example 4
A functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke is a geopolymer loaded with chitosan and copper ions, and is prepared by the following steps:
s1, adding 1g of chitosan into 100ml of mixed solution containing 0.1mol of sodium hydroxide and 1.5g of sodium silicate, and stirring for 2 hours at normal temperature to obtain alkali-activated solution;
s2, adding 2g of nano clay into the alkali-activated solution, performing ultrasonic dispersion for 45min, then reacting for 1h at 40 ℃, and drying the reaction product for 48h at 80 ℃ to obtain a geopolymer composite matrix;
s3, soaking the geopolymer composite matrix in a nickel ion solution with the concentration of 1mol/L for 4 hours, stirring the soaking process, and drying the soaked matrix to obtain the functional geopolymer material Cu2+-geopolymer/chitosan。
Example 5
A functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke is a geopolymer loaded with chitosan and nickel ions, and is prepared by the following steps:
s1, adding 1g of chitosan into 100ml of mixed solution containing 0.1mol of sodium hydroxide and 1.5g of sodium silicate, and stirring for 2 hours at normal temperature to obtain alkali-activated solution;
s2, adding 2g of nano clay into the alkali-activated solution, reacting at 40 ℃ for 1h, and drying the reaction product at 80 ℃ for 48h to obtain a geopolymer composite matrix;
s3, soaking the geopolymer composite matrix in nickel ion solution with the concentration of 1mol/L for 4 hours, stirring the soaking process, and drying the soaked matrix to obtain the functional geopolymer material Ni2+-geopolymer/chitosan。
And (3) performance testing: adding the functionalized geopolymer materials obtained in the examples 1-5 into the middle of a cigarette filter according to the addition amount of 30 mg/cigarette, adopting cut tobacco with the same quality to form a cigarette main body with the same specification, then combining the filter respectively added with the functionalized geopolymer materials of the examples 1-5 with the cigarette main body to prepare a cigarette sample,
these cigarette samples were used as a test group and cigarettes without any filter material added to the filter were used as a control group, and the test group and the control group were subjected to the following performance tests:
measurement of cyanic acid adsorption Effect
The cigarette samples of the test group and the control group are placed on a smoking machine to perform a cigarette smoking experiment on the smoking machine according to standard smoking conditions, HCN in the smoke of the cigarette sample is collected and measured according to a tobacco industry standard method of YC/T253-2008 'determination continuous flow method of hydrogen cyanide in mainstream smoke of cigarettes', and the results are shown in the following table:
② cigarette smoking quality test
The cigarette samples of the test group and the control group are manually evaluated according to the method specified in GB5606.4-2005 (part 4 of cigarettes: sensory technical requirements), and the smoking quality of the cigarettes is comprehensively evaluated from multiple aspects of fragrance, aftertaste, offensive odor, irritation and harmony. The results show that: compared with the control group, the cigarette samples of the test group have no obvious difference in smoking quality.
Therefore, the functionalized polymer material can effectively reduce the release amount of hydrocyanic acid in cigarette smoke, and does not influence the smoking quality of cigarettes.
This detailed description is to be construed as illustrative only and is not to be taken as limiting the invention, as any changes that may be made by a person skilled in the art after reading the present specification will be protected by the patent laws within the scope of the appended claims.
Claims (8)
1. A functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke is characterized in that: the functionalized geopolymer material is a geopolymer loaded with chitosan and metal ions;
the functionalized geopolymer material is obtained by adopting a geopolymer composite matrix synthesized by chitosan, sodium hydroxide, sodium silicate and nano clay, and then soaking the geopolymer composite matrix into a metal ion solution;
the functionalized polymer is prepared by the following steps:
s1, adding chitosan into a mixed solution of sodium hydroxide and sodium silicate, and stirring for 1.5-2.5 hours at normal temperature to obtain an alkali-activated solution, wherein the concentration of the chitosan is 5-15 g/L, and the concentration of the sodium silicate is 10-20 g/L;
s2, adding nano clay into the alkali-activated solution according to the addition amount of 15-25 g/L, reacting at 38-45 ℃ for 0.5-2.0 h, and drying the reaction product to obtain a geopolymer composite matrix;
and S3, dipping the geopolymer composite matrix into the metal ion solution, and drying to obtain the functionalized geopolymer material.
2. The functionalized polymer material for reducing hydrocyanic acid in cigarette smoke according to claim 1, wherein: the metal ions are nickel ions.
3. The functionalized polymer material for reducing hydrocyanic acid in cigarette smoke according to claim 1, wherein: in step S1, the concentration of sodium hydroxide in the mixed solution is 0.5-1.5 mol/L.
4. The functionalized polymer material for reducing hydrocyanic acid in cigarette smoke according to claim 1, wherein: in step S2, after the nanoclay is added with the alkali-activated solution, the nanoclay is subjected to ultrasonic dispersion for 0.5-1 hour and then subjected to reaction.
5. The functionalized polymer material for reducing hydrocyanic acid in cigarette smoke according to claim 1, wherein: in step S2, the drying temperature is 75-85 ℃ and the drying time is 40-60 h.
6. The functionalized polymer material for reducing hydrocyanic acid in cigarette smoke according to claim 1, wherein: in the step S3, the concentration of metal ions in the metal ion solution is 0.5-2 mol/L, the geopolymer composite matrix is soaked in the metal ion solution for 3-5 h, and the soaking process is accompanied with stirring.
7. The application of the functionalized geopolymer material for reducing hydrocyanic acid in cigarette smoke of any one of claims 1 to 6 in cigarettes is characterized in that: the method is characterized in that a functionalized polymer material is added into the cigarette filter tip, and the addition amount is 10-40 mg/cigarette.
8. The use of the functionalized polymer material for reducing hydrocyanic acid in cigarette smoke according to claim 7 in cigarettes, wherein: the functionalized polymer material is added in the middle of the filter.
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