CN110385111B - Mesoporous alumina chitosan-loaded composite material for cigarettes, preparation method and application of mesoporous alumina chitosan-loaded composite material in reducing carbonyl compounds in mainstream smoke - Google Patents

Mesoporous alumina chitosan-loaded composite material for cigarettes, preparation method and application of mesoporous alumina chitosan-loaded composite material in reducing carbonyl compounds in mainstream smoke Download PDF

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CN110385111B
CN110385111B CN201810370962.4A CN201810370962A CN110385111B CN 110385111 B CN110385111 B CN 110385111B CN 201810370962 A CN201810370962 A CN 201810370962A CN 110385111 B CN110385111 B CN 110385111B
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chitosan
mesoporous alumina
composite material
acid
cigarettes
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CN110385111A (en
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谢国勇
袁鼎浩
樊娜
王亮
秦亮生
银董红
尹双凤
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China Tobacco Hunan Industrial Co Ltd
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    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
    • A24B15/302—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances by natural substances obtained from animals or plants
    • 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
    • A24D3/061—Use of materials for tobacco smoke filters containing additives entrapped within capsules, sponge-like material or the like, for further release upon smoking
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates

Abstract

The invention belongs to the field of cigarette materials, and particularly discloses a mesoporous alumina chitosan-loaded composite material for cigarettes, which comprises aminated mesoporous alumina with amino modified on the surface, a polyacid compound grafted through the amino, and chitosan grafted through acid radicals of the polyacid compound. The invention also discloses a preparation method and an application method of the composite material. The invention provides a composite material with a special structure, and researches show that the composite material has an unexpected adsorption effect on carbonyl compounds in mainstream smoke. In addition, the material also has the advantages of cheap and easily obtained raw materials, no toxicity, environmental protection, simple preparation process, low energy consumption and no pollution.

Description

Mesoporous alumina chitosan-loaded composite material for cigarettes, preparation method and application of mesoporous alumina chitosan-loaded composite material in reducing carbonyl compounds in mainstream smoke
Technical Field
The invention relates to the field of cigarette mainstream smoke adsorbing materials, in particular to an adsorbent capable of well adsorbing carbonyl compounds in mainstream smoke.
Background
The cigarette mainstream smoke contains various harmful substances, mainly comprising carbon monoxide, aromatic amines, volatile aldehyde ketone substances, volatile nitrosamines, nitric oxides, ammonia, pyridine and the like. The volatile aldehyde ketone substance is a gas with strong pungent smell, has cilium toxicity, can generate strong stimulation to taste organs and respiratory system of a human body in the cigarette smoking process, is an inhibitor in the lung clearing process, and can cause serious harm to the human body after long-term inhalation.
In the prior art, researches on how to reduce the content of carbonyl compounds in cigarette smoke have been reported, for example, Caocai et al report that an adsorption material with a composite pore structure is prepared by a hydrothermal synthesis method and is used for adsorbing harmful substances such as crotonaldehyde in mainstream smoke, and the selective adsorption rate of the material on the crotonaldehyde under the optimal preparation condition can reach 32%. Chinese patent 201510071429.4 provides a composite material for selectively reducing aldehydes in cigarette smoke, which is prepared by activating porous materials such as activated carbon, molecular sieve, zeolite, resin, silica gel, sepiolite, montmorillonite, diatomite, attapulgite, expanded tobacco stems and the like, and then respectively self-assembling the activated porous materials with anionic polyelectrolyte and cationic polyelectrolyte, wherein the selective adsorption rate of the materials on crotonaldehyde can also reach about 20-32%. The mesoporous alumina provided by von geysear et al can effectively and selectively adsorb carbonyl compounds in mainstream smoke of cigarettes, the addition amount of the mesoporous alumina in each cigarette is 80 mg/cigarette, and the maximum adsorption rate of crotonaldehyde is up to 59.5%. However, the method still has the problems of large adsorbent dosage, certain toxicity of reaction raw materials, long preparation period, unsuitability for large-scale production and the like.
Disclosure of Invention
In order to solve the problems of large adsorbent dosage, certain toxicity of reaction raw materials, long preparation period, unsuitability for large-scale production and the like in the prior art, the invention provides a mesoporous alumina chitosan-loaded composite material for cigarettes.
The second purpose of the invention is to provide a preparation method of the mesoporous alumina-chitosan-loaded composite material.
The third purpose of the invention is to provide the application of the mesoporous alumina chitosan-loaded composite material in reducing the carbonyl compounds of cigarettes.
The mesoporous alumina loaded chitosan composite material for the cigarettes comprises aminated mesoporous alumina with amino modified on the surface, a polybasic acid compound grafted through the amino, and chitosan grafted through acid radicals of the polybasic acid compound.
The invention provides a composite material with a special structure, and researches show that the composite material has an unexpected adsorption effect on carbonyl compounds in mainstream smoke. In addition, the material also has the advantages of cheap and easily obtained raw materials, no toxicity, environmental protection, simple preparation process, low energy consumption and no pollution.
The mesoporous alumina chitosan-loaded composite material for the cigarettes comprises mesoporous alumina, an ammonia base layer (namely aminated mesoporous alumina, also called as ammonia-modified mesoporous alumina) modified on the mesoporous alumina, an acid layer connected through amino groups of the ammonia base layer, and a chitosan layer connected through acid group modification of the acid layer.
In the invention, an amino layer rich in amino is formed on mesoporous alumina in advance, the amino layer is modified by amido bond to form an acid layer modified on the periphery of the mesoporous alumina, the acid layer contains acid group, and the acid group of the acid layer and-NH of chitosan are used for modifying the acid layer2Reacting, and modifying chitosan at the periphery of the acid layer through amido bond.
The composite material has the following structural schematic:
Figure GDA0001694027800000021
the acid layer is a connecting layer, and the mesoporous alumina modified by ammonia and the chitosan are connected through amidation reaction.
Preferably, the number of acid groups of the polybasic acid compound is not less than two.
More preferably, the acid radical of the polybasic acid compound is at least one of carboxylate, phosphate or sulfonate.
The chitosan is also allowed to be grafted with a polybasic acid compound, and the grafted chitosan is continued by the acid group of the polybasic acid compound.
Preferably, the chitosan grafted with the polybasic acid compound is a repeating unit, and the number of the repeating units is 1-5, wherein the chitosan is continuously grafted by acid radicals of the polybasic acid compound.
That is, in the composite material, the chitosan layer is allowed to be modified with an acid layer, and each acid layer is modified with the chitosan layer. In the invention, the acid layer can be continuously modified on the chitosan layer, but the modified acid layer needs to be continuously modified on the chitosan layer; that is, the chitosan layer is the outermost layer of the composite material of the present invention. The composite material is prepared from mesoporous alumina, an amino layer plus (an acid layer plus a chitosan layer) n; n is the repeated number of the acid layer and the chitosan layer; and n is an integer not less than 1.
Preferably, the particle size of the composite material is 40-60 meshes.
Preferably, the specific surface area of the composite material is 320-455 m2(iv)/g, more preferably 442.4 to 452.5m2/g。
The invention also provides a preparation method of the mesoporous alumina chitosan-loaded composite material for cigarettes, which comprises the following steps:
step (1): carrying out amination pretreatment on mesoporous alumina to obtain aminated mesoporous alumina (an ammonia base layer is formed by modifying mesoporous alumina);
step (2): reacting aminated mesoporous alumina with a polybasic acid compound to obtain mesoporous alumina with a modified surface provided with acid groups (an acid layer is formed on an ammonia base layer by modification);
and (3): and (3) reacting the mesoporous alumina with the surface modified with the acid group obtained in the step (2) with chitosan (modifying the acid layer to form a chitosan layer), so as to obtain the mesoporous alumina chitosan-loaded composite material for the cigarette.
According to the method, mesoporous alumina is used as a substrate, and chitosan and the mesoporous alumina are subjected to load combination through the layer-by-layer modification method, so that the obtained product is adsorbed by fully utilizing the functional group specificity of the mesoporous material and the chitosan, and the product shows specific adsorption performance on low-molecular carbonyl compounds in cigarette smoke.
The invention discovers that the preparation method of mesoporous alumina can be used for unexpectedly preparing the composite material with excellent adsorption performance to mainstream smoke, which is different from the conventional porous carrier. The inventor's technology development early attempts to other kinds of porous materials, such as activated carbon, were difficult to obtain the intended technical effect. By adopting mesoporous alumina to be matched with the layer-by-layer modification method, the method has a synergistic effect, and can unexpectedly improve the specific adsorption effect on carbonyl compounds in the mainstream smoke.
According to the invention, the mesoporous alumina is modified with the ammonia base layer, the acid layer connected with the amino of the ammonia base layer and the chitosan layer are modified and connected with the acid layer to prepare the composite material, so that the adsorption rate of the low-molecular aldehyde ketone compound in the cigarette smoke is improved. The preparation process is simple, the preparation process is environment-friendly, and the environment is not polluted. The raw materials related to the technical scheme of the invention are nontoxic, cheap and easily available, the preparation period is greatly shortened by modifying the ammonia-based layer on the mesoporous alumina, the acid layer connected through the amino group of the ammonia-based layer, the chitosan layer connected through the modification of the acid layer, and the like, and the mass production can be realized.
Preferably, the particle size of the mesoporous alumina is 40-60 meshes.
More preferably, the mesoporous alumina has a thickness of 240-460 m2(ii)/g; more preferably, the specific surface area is 241.1 to 455.3m2/g。
Researches show that by adopting the mesoporous alumina under the parameters and utilizing the layer-by-layer modification method disclosed by the invention, the adsorption performance of the obtained composite material can be further improved.
Preferably, the mesoporous alumina is obtained by reacting chitosan and alkali liquor to obtain a precursor, and then roasting the precursor. The inventor unexpectedly finds that the mesoporous alumina obtained by the optimal method is more suitable for the layer-by-layer modification method, and contributes to further improving the specific adsorption performance of the obtained product on carbonyl compounds.
Preferably, the preparation of mesoporous alumina comprises the following steps:
step (a): dissolving chitosan in an acid solution to prepare a chitosan solution;
dissolving aluminum salt in deionized water, and adding the prepared chitosan solution to obtain an aluminum salt-chitosan mixed solution;
step (b): dropwise adding the aluminum salt-chitosan mixed solution into an ammonia water solution (alkali liquor), and then stirring for reaction, carrying out solid-liquid separation and drying to obtain the aluminum salt-chitosan composite microspheres;
step (c): the aluminum salt-chitosan composite microspheres are roasted to obtain the mesoporous alumina.
Preferably, in step (a), the acid solution is an acetic acid solution. The concentration of the acid solution is 1-5 v% (volume percentage). Under the preferable concentration of the acid solution, the mesoporous alumina has larger specific surface area and pore size, which is beneficial to promoting the adsorption of the subsequently obtained composite material to the aldehyde ketone compound in the mainstream smoke.
Preferably, in the step (a), the degree of deacetylation of chitosan is 75% to 90%. The adsorption effect is more excellent in this preferable range of the degree of deacetylation.
The aluminum salt is water-soluble salt of Al known in the art such as aluminum acetate, aluminum nitrate nonahydrate and the like.
Preferably, the concentration of the chitosan in the chitosan solution is 0.01-0.1 g/mL; more preferably 0.01 to 0.08 g/mL. Under the preferred chitosan concentration, the obtained mesoporous alumina has better pore volume and specific surface area, and is beneficial to the subsequent modification process and adsorption. Above this concentration, the subsequent preparation is not favored.
The concentration of the aluminum salt in the aluminum salt-chitosan mixed solution is not particularly required.
In the present invention, in the step (b), the alkali solution is preferably ammonia water; further preferably, the concentration of the ammonia water is 12.5 to 28 wt%.
In the step (b), after stirring and reacting (the reaction time is 0.5-2.5 h for example), carrying out solid-liquid separation and drying to obtain the precursor.
In the step (b), adding ammonia water, wherein the stirring speed is 200-1000 r/min as a parameter in the precipitation reaction process; and controlling the pH value of the system to be 8-14 by ammonia water.
The reaction temperature is not particularly limited, and may be, for example, room temperature (15 to 35 ℃ C.).
And (b) drying the material subjected to solid-liquid separation at room temperature, wherein the preferable drying time is 12-72 h.
The inventor also finds that the control of the roasting temperature in the preparation process of the mesoporous alumina is beneficial to preparing the material more suitable for adopting the layer-by-layer modification method.
Preferably, the firing is performed in an air atmosphere.
Preferably, the roasting temperature is 500 to 550 ℃. Under the optimized roasting temperature, the chitosan in the obtained mesoporous alumina is removed more thoroughly, and the modification and adsorption performance is more excellent.
The heating rate in the roasting process is preferably 1-10 ℃/min; further preferably 5 ℃/min.
Preferably, the heat preservation roasting time is 1.5-5 h at the roasting temperature.
The invention discloses a preparation method of preferable mesoporous alumina, which comprises the following steps:
step (a): dissolving chitosan in 1-5 v% acetic acid solution, and uniformly stirring and mixing to obtain chitosan solution;
dissolving aluminum nitrate nonahydrate in deionized water, stirring and mixing uniformly, and then adding a chitosan solution with the deacetylation degree of 75-90% and a 5 v% acetic acid solution with the deacetylation degree of 1.5-3 g/50 ml; stirring and mixing uniformly to prepare an aluminum salt-chitosan mixed solution;
step (b): dropwise and slowly adding the aluminum salt-chitosan mixed solution into the ammonia water solution, stirring for reaction, wherein the pH of a reaction system is 8-14, filtering and drying to obtain aluminum salt-chitosan composite microspheres;
a step (c): and (3) placing the aluminum salt-chitosan composite microspheres in a clean crucible, roasting for 1.5-5 h at 500-550 ℃, grinding, and screening for 40-60 meshes to obtain the mesoporous alumina with a certain particle size.
Researches find that the mesoporous alumina prepared by the method has better adsorption property by adopting the layer-by-layer modification method of the method, and is more suitable for being applied to cigarettes.
In the invention, in the step (1), mesoporous alumina is placed in an ammonia water solution, and then the aminated mesoporous alumina is obtained through stirring, solid-liquid separation, washing and drying.
Preferably, in the step (1), the concentration of the ammonia water is 12.5-28 wt%; the soaking time in ammonia water is 0.5-4.5 h. Preferably, the temperature of the soaking process is 20-35 ℃.
In the step (1), washing contributes to further improvement of the adsorption performance of the obtained composite material. Washing is not particularly required, preferably, the washing liquid is deionized water, the washing times are 3-5 times, and the drying temperature is 20-40 ℃. In the washing process, the washing method has no special requirement, for example, the liquid-solid ratio in the washing process is 10-100 mL (washing liquid, namely water)/g. Preferably until the pH of the wash liquor is near neutral.
According to the invention, through the amination pretreatment, through the pore diameter and material characteristics of mesoporous alumina, through a chemical and physical synergistic manner, amino groups are modified on the mesoporous alumina.
In the invention, the aminated mesoporous alumina is placed in a solution dissolved with a polybasic acid compound, and after stirring reaction, solid-liquid separation and washing are carried out to obtain the mesoporous alumina modified with acid groups.
In the invention, the aminated mesoporous alumina is modified with a polybasic acid compound in advance through a physical and chemical method, namely, a surface modification group of the mesoporous alumina is converted into an acid group, and the acid group reacts with an amino group or a hydroxyl group of chitosan, so that the chitosan is modified on the surface of the mesoporous alumina; the polybasic acid compound serves as a tie to connect the mesoporous alumina and the chitosan. It is necessary that the polyacid compound has multiple reaction sites.
Preferably, the polybasic acid compound is a compound containing not less than two acid groups; the acid radical is phosphate radical and/or carboxylate radical.
Preferably, the polyacid compound is at least one acid or acid salt of polyphosphoric acid, dibasic organic carboxylic acid, polybasic organic carboxylic acid, acidic amino acid, and the like.
Further preferably, the polyacid compound is polyphosphoric acid. The effect of adopting phosphate radical is better.
Preferably, the polybasic acid compound is sodium tripolyphosphate, aluminum tripolyphosphate, potassium tripolyphosphate, itaconic acid, succinic acid, humic acid, polyglutamic acid, polyaspartic acid and the like.
Preferably, the solution of the polybasic acid compound has an acid concentration of 1 to 5 wt%.
Preferably, in the step (2), the time for soaking the aminated mesoporous alumina in the solution of the polybasic acid compound is 0.5-1.5 h; the temperature of the soaking process is preferably 20-35 ℃.
In the step (2), the washing liquid is deionized water, and the washing times are 3-5 times. The drying temperature is 20-40 ℃.
In step (2), washing helps to further improve the adsorption performance of the resulting material. The washing method has no special requirement, for example, the liquid-solid ratio in the washing process is 10-100 mL/g. Preferably until the pH of the wash liquor is near neutral.
Preferably, step (3): and (3) soaking the mesoporous alumina modified with acid groups on the surface obtained in the step (2) in a solution dissolved with chitosan, stirring for reaction, and then carrying out solid-liquid separation, washing and drying to obtain the mesoporous alumina loaded chitosan composite material for cigarettes.
Preferably, step (3): the deacetylation degree of the chitosan is 75-90%. The adsorption effect is more excellent in this preferred range of the degree of deacetylation.
Preferably, in the step (3), the chitosan solution is obtained by dissolving chitosan in an acid solution, wherein the concentration of chitosan is 0.01-0.1 g/mL, and more preferably 0.01-0.08 g/mL. Under the preferred chitosan concentration, the obtained mesoporous alumina has better pore size, pore volume and specific surface area, and is beneficial to the subsequent modification process and adsorption. Above this concentration, dissolution is difficult and subsequent preparation is not facilitated.
Preferably, in the step (3), the acid solution is an acetic acid solution; the concentration of the acid solution is 1-5 v%. At the preferred acid solution concentration, the mesoporous alumina has a larger specific surface area and pore size, which is beneficial to the adsorption of the aldehyde ketone compound.
Preferably, in the step (3), the washing solution is deionized water, the washing times are 3-5 times, and the drying temperature is 20-40 ℃.
In step (3), washing helps to further improve the adsorption performance of the resulting material. The washing method has no special requirement, for example, the liquid-solid ratio in the washing process is 10-100 mL/g. Preferably until the pH of the wash liquor is near neutral.
In the present invention, steps (2) and (3) are repeated.
The inventor researches and discovers that the modified polybasic acid compound and the chitosan form a layer, and the number of layers of the group modified layer by layer is controlled, so that the specific adsorption performance of the carbonyl group of the mainstream smoke can be further improved.
Preferably, the number of repetitions is not higher than 5. Researches show that the adsorption performance is better when the steps (2) and (3) are carried out in a circulating way for no more than 5 times, and the number of circulating layers is further increased, which is not beneficial to the improvement of the adsorption performance. More preferably, the number of repetitions is 2 to 4.
The invention also discloses the mesoporous alumina chitosan-loaded composite material for the cigarettes prepared by the preparation method.
The composite material comprises mesoporous alumina, an ammonia base layer modified on the mesoporous alumina, an acid layer connected through amino groups of the ammonia base layer, and a chitosan layer modified and connected through the acid layer.
Preferably, the chitosan layer is allowed to be modified with an acid layer, and each acid layer is modified with a chitosan layer.
Preferably, the particle size of the composite material is 40-60 meshes; the specific surface area is 442.4 to 452.5m2/g。
The invention also discloses application of the mesoporous alumina chitosan-loaded composite material for cigarettes, which is added into cigarettes and used for reducing carbonyl compounds in mainstream smoke.
According to the composite material, chitosan is modified on the outer layer of the mesoporous alumina through the layer-by-layer modification process. The composite material has good chemical adsorption performance of a modified material and good physical adsorption performance endowed by the structural characteristics, and achieves the effect of synergistically improving the excellent adsorption effect of carbonyl compounds in mainstream smoke through the physical and chemical effects.
The composite material has good adsorption effect, does not increase the suction resistance, and is particularly suitable for being added into cigarettes to reduce the content of carbonyl compounds in mainstream smoke.
Preferably, the application of the invention is to add the composite material into a cigarette filter.
Preferably, the round rod added with the composite material is prepared and compounded with a common fiber round rod to form a binary filter stick for a cigarette filter.
The composite material is adopted to prepare a binary filter stick by adopting the conventional method, wherein one side of the binary filter stick is added with the composite material part, and the other end of the binary filter stick is a conventional filter stick fiber part.
Further preferably, in the binary filter stick, the part added with the composite material is close to the tobacco shred end.
Preferably, the addition amount of the composite material is 10-40 mg/piece.
Preferably, the carbonyl compound is at least one of formaldehyde, acetaldehyde, acetone, acrolein, crotonaldehyde, propionaldehyde, 2-butanone and butyraldehyde.
The inventor unexpectedly finds that the composite material provided by the invention has better adsorption performance on crotonaldehyde.
The invention has the advantages that:
1. according to the invention, chitosan is selected as cationic polyelectrolyte, and abundant functional groups such as amino groups, hydroxyl groups and the like have good adsorption performance on crotonaldehyde;
2. according to the invention, a multi-stage acid (such as sodium tripolyphosphate) is selected as an anionic polyelectrolyte, so that the water-retaining property is good, and the chitosan-containing water-retaining agent can be efficiently combined with chitosan, thereby being beneficial to further improving the adsorption effect on carbonyl compounds;
3. the raw materials selected by the invention are cheap and easy to obtain, and the technical method has mild conditions;
4. the preparation process is simple, and the required equipment is simple and convenient;
5. the invention has no pollution to the environment and high production efficiency;
6. the invention fully utilizes the physical adsorption of mesoporous alumina and the specific adsorption of functional groups on chitosan, and has better adsorption effect on carbonyl compounds (such as acrolein, crotonaldehyde and other substances) in the cigarette smoke.
Drawings
FIG. 1 is a graph showing the adsorption and desorption curves of N2 for mesoporous alumina and its composite material prepared in example 1;
FIG. 2 is a graph showing the pore size distribution of mesoporous alumina and its composite material prepared in example 1;
FIG. 3 is a schematic view showing the manner of adding mesoporous alumina and its composite material to a cigarette filter;
FIG. 4 is a scanning electron micrograph of the mesoporous alumina prepared in example 1 and its composite;
FIG. 5 is an infrared spectrum of the raw material and the composite material thereof in example 2;
FIG. 6 is a transmission electron micrograph of the mesoporous alumina and the composite thereof according to example 1.
In the context of figure 1 of the drawings,meso-Al2O3represents aminated mesoporous alumina modified with an amino group, (STPP/Ch)1～(STPP/Ch)5Respectively representing the number of the modified acid layer and the chitosan layer; as can be seen from fig. 1, the mesoporous alumina composite material modified by the acid layer and the chitosan layer still has a mesoporous structure.
In fig. 2, as the number of modified acid layers and chitosan layers increases, the peak position of the pore size distribution curve gradually decreases, but the range of the abscissa where the peak position is located is not changed basically, which indicates that the layer-by-layer electrostatic self-assembly process has a relatively obvious influence on the pore structure of the material, especially the pore volume thereof.
In fig. 3: a-a composite adsorbent; b-acetate fiber filter stick; 1-segmenting a filter stick; 2-tipping paper; 3-tipping paper.
In FIG. 4, (a) and (b) show the scanning electron micrographs of the amino group-modified mesoporous alumina at 50 μm and 10 μm, respectively; (c) and (d) scanning electron micrographs of the composite material modified with the three acid layers and the chitosan layer at 50 μm and 10 μm, respectively; (e) and (f) respectively show scanning electron micrographs of the composite material modified with the five-layered acid layer and the chitosan layer under 50 micrometers and 10 micrometers; as can be seen from fig. 4, a large number of pore structures exist on the surface of the mesoporous alumina and the composite material thereof, which are beneficial for the entry of low-molecular aldehydes and ketones in the mainstream smoke, and are combined with functional groups such as amino groups and hydroxyl groups on the surface of the mesoporous alumina and the composite material thereof to enhance the adsorption effect of the mesoporous alumina and the composite material thereof. Along with the increase of the number of the modified acid layer and the chitosan layer, the pores on the surface of the material are gradually occupied and reduced, and the blocked pores are not beneficial to the entry of low-molecular aldone.
In fig. 5, a is Ch (chitosan), b is STPP (sodium tripolyphosphate), c is MA (mesoporous alumina), and d is MA @ STPP/Ch (composite material), which respectively represent chitosan, sodium tripolyphosphate, mesoporous alumina, and a composite material modified with a sodium tripolyphosphate layer and a chitosan layer; as can be seen from FIG. 5, Ch and MA @ STPP/Ch are at 3400cm-1The two peaks are obvious on the left and the right, and are multiple absorption peaks widened by overlapping the-OH stretching vibration absorption peak forming hydrogen bond association with the vibration absorption peak of-NH. Ch molecules have a large number of hydrogen bonds, and the peak of the Ch molecules is caused to be different in length and strength of the hydrogen bondsOver a wide frequency range. The curve of the 4 group in the figure is 1643cm-1The peak intensity of MA @ STPP/Ch and Ch is obviously higher than that of other two groups of curves, which is the bending vibration absorption peak of N-H bond in primary amide. MA @ STPP/Ch and Ch at 1600cm-1Another characteristic absorption peak of bending vibration at which there is an N-H bond. Ch. MA and composite material MA @ STPP/Ch of MA and STPP/Ch are at 1403cm-1And a characteristic absorption peak of a C-N bond is arranged at the left and the right. Furthermore, MA @ STPP/Ch was at 1044cm-1A peak similar to Ch appears at the left and right, which is a characteristic absorption peak of a C-O bond in secondary alcohol; at 1157cm at the same time-1、892cm-1A characteristic absorption peak similar to STPP appears. This demonstrates that the sodium tripolyphosphate layer and the chitosan layer are successfully modified on the aminated mesoporous alumina.
Detailed Description
As shown in figure 3, the mesoporous alumina and the composite material thereof provided by the invention are added into a cigarette filter in a manner that a material A section (the composite material provided by the invention is added into the A section) is added between two sections of B sections of common acetate fiber filter cores to form a binary composite filter stick. The filter stick is composed of a composite filter element 1 of a filter element A section and a filter element B section, an inner wrapping layer 2 and an outer wrapping layer 3. The addition amount of the material in the filter tip is 10-40 mg.
The following examples, unless otherwise stated, have degrees of deacetylation of 75% to 90%.
In the following examples, percentages refer to percent by mass unless otherwise indicated.
Example 1
Step (1): preparation of aminated mesoporous alumina
The invention prepares regular and uniform mesoporous alumina by changing the concentration of chitosan solution:
step (a): weighing 4g of chitosan, dissolving the chitosan in 50ml of 5 v% acetic acid solution, and stirring at a high speed for 1 hour at normal temperature to obtain a chitosan solution; the chitosan concentration was 0.08 g/mL.
3.75g of Al (NO) are weighed out3)3·9H2And O, dissolving in 20ml of deionized water, and performing ultrasonic treatment for 15min to obtain an aluminum salt solution.
The aluminum salt solution and the chitosan solution are mixed and stirred for 1 hour.
Step (b): diluting the concentrated ammonia water and the deionized water according to the volume ratio of 1: 1 to obtain an ammonia water solution.
And dropwise adding the mixed solution into an ammonia water solution (the dosage is 500ml, the pH value in the reaction process is controlled to be 8-14, the stirring speed is 600 r/min), keeping stirring at normal temperature, and continuously stirring for 1h to obtain the aluminum source-chitosan precursor.
Step (c): and separating an aluminum source-chitosan precursor, naturally drying for 72h, heating to 550 ℃ at the speed of 5 ℃/min in an air atmosphere, and calcining for 1.5h to obtain the mesoporous alumina material.
Soaking the mesoporous alumina material in 12.5% ammonia water solution for 3h, filtering, and washing (the washing method is washing with 100ml/g deionized water for 3 times) to obtain aminated mesoporous alumina;
step (2): soaking aminated mesoporous alumina in a 1 wt% sodium tripolyphosphate solution, then stirring (the time is 1h, and the temperature is 20-35 ℃), filtering, washing (the washing method is 100ml/g deionized water washing for 3 times), and obtaining sodium tripolyphosphate-aminated mesoporous alumina;
and (3): soaking sodium tripolyphosphate-aminated mesoporous alumina in 0.01g/ml chitosan solution, stirring (the time is 1h, and the temperature is 20-35 ℃), filtering, and washing (the washing method is 100ml/g deionized water washing for 3 times), so as to obtain the mesoporous alumina supported sodium tripolyphosphate/chitosan composite material;
taking the mesoporous alumina loaded chitosan composite material, and repeating the steps (2) and (3) for three times; and finally, washing and drying to obtain the three-layer modified mesoporous alumina supported chitosan composite material.
The composite material is added into a filter tip to form a composite filter stick according to the adding mode (as shown in figure 3, the adding amount of the composite material is 40 mg).
By using N2The mesoporous alumina and the mesoporous alumina composite material are subjected to adsorption and desorption testing, the specific surface area of the mesoporous alumina and the mesoporous alumina composite material is tested by adopting BET (BET area), and the following data are obtained:
the average pore diameter of the mesoporous alumina is 5.20nm, and the specific surface area is 455.3m2(ii)/g; composite material flatThe average pore size is 5.59nm, and the specific surface area is 448.6m2/g。
Analyzing and obtaining the content and the adsorption rate of the carbonyl compound in the cigarette smoke by adopting a high performance liquid chromatography:
TABLE 1 adsorption amount (μ g/cig) and adsorption rate (%)
Figure GDA0001694027800000111
Example 2
The only difference compared with example 1 is that in step (2) and step (3), only the number of modified layers was changed to five, that is, step (2) and step (3) were sequentially repeated 5 times.
By using N2The mesoporous alumina and the mesoporous alumina composite material are subjected to adsorption and desorption testing, the specific surface area of the mesoporous alumina and the mesoporous alumina composite material is tested by adopting BET (BET area), and the following data are obtained:
the average pore diameter of the mesoporous alumina is 5.20nm, and the specific surface area is 455.3m2(ii)/g; the average pore size of the composite material is 5.42nm, and the specific surface area is 442.4m2/g。
Analyzing and obtaining the content and the adsorption rate of the carbonyl compound in the cigarette smoke by adopting a high performance liquid chromatography:
table 2 adsorption amount (. mu.g/cig) and adsorption ratio (%)
Figure GDA0001694027800000121
Example 3
The only difference compared to example 1 is that in step (a), only the chitosan content was changed to 2.5 g. The chitosan concentration was 0.05 g/mL.
By using N2The mesoporous alumina and the mesoporous alumina composite material are subjected to adsorption and desorption testing, the specific surface area of the mesoporous alumina and the mesoporous alumina composite material is tested by adopting BET (BET area), and the following data are obtained:
the average pore diameter of the mesoporous alumina is 3.77nm, and the specific surface area is 324.7m2(iv) g; composite average pore size 412nm, specific surface area 320.3m2/g。
Table 3 adsorption amount (. mu.g/cig) and adsorption ratio (%)
Figure GDA0001694027800000122
Example 4
The only difference compared to example 3 is that, in step (a), only the acetic acid solution concentration was changed to 3 v%.
By using N2The mesoporous alumina and the mesoporous alumina composite material are subjected to adsorption and desorption testing, the specific surface area of the mesoporous alumina and the mesoporous alumina composite material is tested by adopting BET (BET area), and the following data are obtained:
the average pore diameter of the mesoporous alumina is 6.12nm, and the specific surface area is 321.3m2(ii)/g; the average pore size of the composite material is 6.67nm, and the specific surface area is 317.5m2/g。
TABLE 4 adsorption amount (. mu.g/cig) and adsorption ratio (%)
Figure GDA0001694027800000131
Example 5
Compared with example 1, the only difference is that in step (2), only the polybasic acid compound is changed to gamma-polyglutamic acid.
And adding the composite material into a filter tip according to the adding mode to form a composite filter stick, wherein the adding amount of the composite material is 40 mg.
By the use of N2The mesoporous alumina and the mesoporous alumina composite material are subjected to adsorption and desorption testing, the specific surface area of the mesoporous alumina and the mesoporous alumina composite material is tested by adopting BET (BET area), and the following data are obtained:
the average pore diameter of the mesoporous alumina is 5.20nm, and the specific surface area is 455.3m2(iv) g; the average pore size of the composite material is 4.49nm, the specific surface area is 302.8m2/g。
TABLE 5 adsorption amount (μ g/cig) and adsorption rate (%)
Figure GDA0001694027800000132
Example 6
The only difference compared with example 1 is that in step (c), only the firing temperature was changed to 500 ℃.
And adding the composite material into a filter tip according to the adding mode to form a composite filter stick, wherein the adding amount of the composite material is 40 mg.
By using N2The mesoporous alumina and the mesoporous alumina composite material are subjected to adsorption and desorption testing, the specific surface area of the mesoporous alumina and the mesoporous alumina composite material is tested by adopting BET (BET area), and the following data are obtained:
the average pore diameter of the mesoporous alumina is 3.02nm, and the specific surface area is 195.6m2(iv) g; the average pore size of the composite material is 2.96nm, and the specific surface area is 271.3m2/g。
TABLE 6 adsorption amount (μ g/cig) and adsorption rate (%)
Figure GDA0001694027800000141
Comparative example 1:
compared with example 1, the difference is that the mesoporous alumina is subjected to amino modification in the absence of the step (1).
And adding the composite material into a filter tip according to the adding mode to form a composite filter stick, wherein the adding amount of the composite material is 40 mg.
By using N2The pore diameter distribution of the mesoporous alumina and the mesoporous alumina composite material is tested by adsorption and desorption, and the specific surface area of the mesoporous alumina and the mesoporous alumina composite material is tested by BET (BET surface area) to obtain the following data:
the average pore diameter of the mesoporous alumina is 5.20nm, and the specific surface area is 455.3m2(ii)/g; the average pore size of the composite material is 5.07nm, the specific surface area is 429.73m2/g。
Table 7 adsorption amounts (. mu.g/cig) and adsorption ratios (%)
Figure GDA0001694027800000142
Lack of amino layer modification of mesoporous alumina, subsequent acid layer modification and chitosan layer modification cannot be effectively carried out, and the adsorption effect of the material on the aldehyde ketone compound cannot be obviously improved.
Comparative example 2:
the difference compared to example 1 is the absence of a washing step between step (2) and step (3) and their repetition.
And adding the composite material into a filter tip according to the adding mode to form a composite filter stick, wherein the adding amount of the composite material is 40 mg.
By using N2The mesoporous alumina and the mesoporous alumina composite material are subjected to adsorption and desorption testing, the specific surface area of the mesoporous alumina and the mesoporous alumina composite material is tested by adopting BET (BET area), and the following data are obtained:
the average pore diameter of the mesoporous alumina is 5.20nm, and the specific surface area is 455.3m2(ii)/g; the average pore size of the composite material is 3.11nm, and the specific surface area is 478.2m2/g。
TABLE 8 adsorption amount (. mu.g/cig) and adsorption ratio (%)
Figure GDA0001694027800000151
And (3) a washing step is lacked between the step (2) and the step (3), so that the modified composite material is blocked by an acid layer and a chitosan layer, the pore diameter of the material is reduced, and the adsorption effect of the material on the aldehyde ketone compound is not obviously improved.
Comparative example 3:
according to the contrast scheme, home-made mesoporous alumina is replaced by commercially available and porous activated carbon (Hongshu environmental protection factory shop, 60-100 mesh food grade), and the activated carbon modified chitosan composite material is prepared by modifying the activated carbon modified chitosan according to the steps (1), (2) and (3).
And adding the composite material into a filter tip according to the adding mode to form a composite filter stick, wherein the adding amount of the composite material is 40 mg.
TABLE 9 adsorption amount (. mu.g/cig) and adsorption ratio (%)
Figure GDA0001694027800000152
Figure GDA0001694027800000161
Through the embodiment and the proportion, the mesoporous alumina prepared by the method is matched with the modification method, so that the adsorption material with excellent performance can be obtained; in particular, the mesoporous alumina obtained at a proper chitosan concentration and precursor roasting temperature in the step (a) can unexpectedly further improve the adsorption performance of the composite material modified by the method. Researches find that the composite material obtained by modifying aminated mesoporous alumina with sodium tripolyphosphate and chitosan in a preferred range has a good adsorption effect on aldehyde ketone compounds in main stream smoke of cigarettes, and is obviously superior to aminated mesoporous alumina.

Claims (31)

1. The mesoporous alumina chitosan-loaded composite material for the cigarettes is characterized by comprising aminated mesoporous alumina with amino modified on the surface, a polyacid compound grafted through the amino and chitosan grafted through acid radicals of the polyacid compound;
the mesoporous alumina chitosan-loaded composite material for the cigarettes is prepared by the following steps:
step (1): placing mesoporous alumina in an ammonia water solution, then stirring, carrying out amination pretreatment, and then carrying out solid-liquid separation, washing and drying to obtain aminated mesoporous alumina; the mesoporous alumina is obtained by reacting chitosan and alkali liquor to obtain a precursor, and then roasting the precursor; the roasting temperature is 500-550 ℃; the particle size of the mesoporous alumina is 40-60 meshes; the specific surface area is 240-460 m2/g；
Step (2): putting aminated mesoporous alumina into a solution in which a polybasic acid compound is dissolved, reacting with the polybasic acid compound, and then carrying out solid-liquid separation, washing and drying to obtain mesoporous alumina with a modified acid group on the surface; the acid radical number of the polybasic acid compound is not less than two; the acid radical of the polybasic acid compound is at least one of carboxylate, phosphate or sulfonate;
and (3): and (3) soaking the mesoporous alumina modified with acid groups on the surface obtained in the step (2) in a solution dissolved with chitosan to react with the chitosan, and then carrying out solid-liquid separation, washing and drying to obtain the mesoporous alumina loaded chitosan composite material for cigarettes.
2. The mesoporous alumina chitosan-loaded composite material for cigarette as claimed in claim 1, wherein chitosan is allowed to be grafted with a polybasic acid compound, and the grafted chitosan is continued through acid groups of the polybasic acid compound.
3. The mesoporous alumina chitosan-loaded composite material for cigarettes as claimed in claim 2, wherein a polybasic acid compound is grafted on chitosan, chitosan which is continuously grafted by acid radicals of the polybasic acid compound is a repeating unit, and the number of the repeating units is 1-5.
4. The mesoporous alumina chitosan-loaded composite material for cigarette as claimed in claim 1, wherein the particle size of the composite material is 40-60 meshes; the specific surface area is 320-455 m2/g。
5. A preparation method of the mesoporous alumina chitosan-loaded composite material for the cigarettes as claimed in any one of claims 1 to 4, is characterized by comprising the following steps:
step (1): placing mesoporous alumina in an ammonia water solution, then stirring, carrying out amination pretreatment, and then carrying out solid-liquid separation, washing and drying to obtain aminated mesoporous alumina; the mesoporous alumina is prepared by reacting chitosan and alkali liquor to obtain a precursor, and then reactingRoasting the precursor to obtain the precursor; the roasting temperature is 500-550 ℃; the particle size of the mesoporous alumina is 40-60 meshes; the specific surface area is 240-460 m2/g；
Step (2): putting aminated mesoporous alumina into a solution in which a polybasic acid compound is dissolved, reacting with the polybasic acid compound, and then carrying out solid-liquid separation, washing and drying to obtain mesoporous alumina with a modified acid group on the surface;
and (3): and (3) soaking the mesoporous alumina modified with acid groups on the surface obtained in the step (2) in a solution dissolved with chitosan to react with the chitosan, and then carrying out solid-liquid separation, washing and drying to obtain the mesoporous alumina loaded chitosan composite material for cigarettes.
6. The preparation method of the mesoporous alumina chitosan-loaded composite material for cigarettes as claimed in claim 5, wherein the preparation of the mesoporous alumina comprises the following steps:
step (a): dissolving chitosan in an acid solution to prepare a chitosan solution;
dissolving aluminum salt in deionized water, and adding the prepared chitosan solution to obtain an aluminum salt-chitosan mixed solution;
step (b): dropwise adding the aluminum salt-chitosan mixed solution into an ammonia water solution, and then stirring for reaction, carrying out solid-liquid separation and drying to obtain the aluminum salt-chitosan composite microspheres;
step (c): the aluminum salt-chitosan composite microspheres are roasted to obtain the mesoporous alumina.
7. The preparation method of the mesoporous alumina-chitosan loaded composite material for cigarette as claimed in claim 6, wherein in the step (a), the acid solution is acetic acid solution; the concentration of the acid solution is 1-5 v%;
the deacetylation degree of the chitosan is 75-90%.
8. The preparation method of the mesoporous alumina chitosan-loaded composite material for cigarettes as claimed in claim 7, wherein the concentration of chitosan in the chitosan solution is 0.01-0.1 g/mL.
9. The preparation method of the mesoporous alumina chitosan-loaded composite material for cigarette as claimed in claim 8, wherein in the step (b), the pH of the reaction system is controlled to be 8-14 by ammonia water.
10. The preparation method of the mesoporous alumina-chitosan loaded composite material for cigarettes as claimed in claim 5, wherein the roasting process is carried out in an air atmosphere, and the roasting time is 1.5-5 h.
11. The preparation method of the mesoporous alumina chitosan-loaded composite material for cigarette as claimed in claim 5, wherein in the step (1), the mesoporous alumina is placed in an ammonia water solution, and then stirring, solid-liquid separation, washing and drying are carried out to obtain the aminated mesoporous alumina.
12. The preparation method of the mesoporous alumina-chitosan loaded composite material for cigarettes as claimed in claim 11, wherein in the step (1), the concentration of the ammonia water is 12.5% -28%; soaking in ammonia water for 0.5-4.5 h;
the temperature of the soaking process is 20-35 ℃.
13. The preparation method of the mesoporous alumina-chitosan-loaded composite material for cigarettes as claimed in claim 5, wherein the polybasic acid compound is a compound containing not less than two acid groups; the acid radical is phosphate radical and/or carboxylate radical.
14. The preparation method of the mesoporous alumina-chitosan loaded composite material for cigarettes as claimed in claim 13, wherein the polyacid compound is at least one acid or acid salt of polyphosphoric acid, dibasic organic carboxylic acid, polybasic organic carboxylic acid and acidic amino acid.
15. The method for preparing the mesoporous alumina-chitosan loaded composite material for cigarettes as claimed in claim 14, wherein the polyacid compound is at least one of sodium tripolyphosphate, aluminum tripolyphosphate, potassium tripolyphosphate, itaconic acid, succinic acid, humic acid, polyglutamic acid, and polyaspartic acid.
16. The preparation method of the mesoporous alumina chitosan-loaded composite material for cigarette as claimed in claim 5, wherein the concentration of acid in the solution of the polyacid compound is 1-5 wt%.
17. The preparation method of the mesoporous alumina loaded chitosan for cigarette as claimed in claim 16, wherein in the step (2), the time for soaking the aminated mesoporous alumina in the solution of the polybasic acid compound is 0.5-1.5 h; the temperature of the soaking process is 20-35 ℃.
18. The preparation method of the mesoporous alumina-chitosan loaded composite material for cigarettes as claimed in claim 17, wherein in the step (2), the washing liquid is deionized water, and the liquid-solid ratio in the washing process is 10-100 mL/g; the washing times are 3-5 times, and the drying temperature is 20-40 ℃.
19. The preparation method of the mesoporous alumina chitosan-loaded composite material for cigarettes as claimed in claim 5, wherein the step (3): the deacetylation degree of the chitosan is 75% -90%.
20. The preparation method of the mesoporous alumina chitosan-loaded composite material for cigarette as claimed in claim 19, wherein in the step (3), chitosan is dissolved in an acid solution to obtain the chitosan solution, wherein the concentration of chitosan is 0.01-0.1 g/mL.
21. The method for preparing the mesoporous alumina-chitosan loaded composite material for cigarettes as claimed in claim 20, wherein in the step (3), the acid solution is an acetic acid solution; the concentration of the acid solution is 1-5 v%.
22. The preparation method of the mesoporous alumina-chitosan loaded composite material for cigarettes as claimed in claim 21, wherein in the step (3), the washing solution is deionized water, the washing times are 3-5 times, and the drying temperature is 20-40 ℃;
the liquid-solid ratio in the washing process is 10-100 mL/g.
23. The preparation method of the mesoporous alumina chitosan for cigarette as claimed in any one of claims 5 to 22, wherein the steps (2) and (3) are repeated.
24. The method for preparing the mesoporous alumina chitosan-loaded composite material for cigarette as claimed in claim 23, wherein the repetition time is not higher than 5 times.
25. The mesoporous alumina chitosan-loaded composite material for the cigarettes prepared by the preparation method of any one of claims 5 to 24.
26. Use of the mesoporous alumina-chitosan for cigarette as claimed in claim 25 as a composite material; the method is characterized in that the method is added into cigarettes and used for reducing carbonyl compounds in mainstream smoke.
27. Use of the mesoporous alumina loaded chitosan for cigarette as claimed in claim 26; the cigarette filter tip is characterized by being added into a cigarette filter tip.
28. Use of the mesoporous alumina chitosan loaded composite material for cigarette as claimed in claim 27; the method is characterized in that a round bar added with the composite material is prepared and is compounded with a common fiber round bar to form a binary filter stick for a cigarette filter.
29. Use of the mesoporous alumina chitosan loaded composite material for cigarette as claimed in claim 28; the method is characterized in that the part added with the composite material in the binary filter stick is close to the tobacco shred end.
30. Use of the mesoporous alumina loaded chitosan for cigarette as claimed in claim 26; the composite material is characterized in that the addition amount of the composite material is 10-40 mg/piece.
31. Use of the mesoporous alumina chitosan for cigarette as claimed in any one of claims 26 to 30; the method is characterized in that the carbonyl compound is at least one of formaldehyde, acetaldehyde, acetone, acrolein, crotonaldehyde, propionaldehyde, 2-butanone and butyraldehyde.
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