CN107252672B - Modified phosphorus-aluminum molecular sieve filter tip adsorption material and preparation method and application thereof - Google Patents
Modified phosphorus-aluminum molecular sieve filter tip adsorption material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a modified phosphorus-aluminum molecular sieve filter tip adsorption material, a preparation method and application thereof, and belongs to the technical field of cigarettes. The adsorption material belongs to a metal Fe modified APO-5 molecular sieve, and the specific preparation steps comprise the steps of preparation, crystallization, drying, roasting and the like of FeAPO-5 initial gel, the prepared adsorption material is a mesoporous APO-5 molecular sieve with uniform aperture, Fe atoms enter an APO-5 framework through lattice substitution, the electronegativity of the Fe atoms is changed, and a B acid site center is generated, and after the Fe atoms are used for preparing a composite filter tip in a cigarette filter tip, the release amount of phenol, HCN and crotonaldehyde in cigarette mainstream smoke can be effectively reduced, so that the adsorption material has good popularization and application values.
Description
Technical Field
The invention belongs to the technical field of cigarettes, and particularly relates to a modified phosphorus-aluminum molecular sieve filter tip adsorption material and a preparation method and application thereof.
Background
With the continuous improvement of living standard of people, the attention of human beings to health and environment is generally strengthened, and the health and environment influence brought by smoking draws more and more attention. The tar and harm reduction of the tobacco organization in the world to cigarettes is highly regarded for a long time, all countries actively respond, the cigarette industry is one of the underpinning industries of the economic development of China, and the market has higher and higher requirements on cigarettes. On the premise of not influencing the sensory comfort of consumers, the harmful ingredients in the cigarette smoke are reduced, which is always a hotspot of the research of the tobacco industry. Adding an adsorption material into a cigarette filter is an effective method.
Phenol, hydrogen cyanide and crotonaldehyde in the smoke belong to harmful components with large negative effects, and are always valued by technologists. However, the research work for reducing the contents of phenol, HCN and crotonaldehyde in the cigarette smoke, which is carried out at home and abroad at present, has little and few requirements for materials capable of simultaneously adsorbing three gases and reducing the contents. The patent CN 104941606A adopts a molecular sieve-polyether sulfone composite material for reducing the content of crotonaldehyde and HCN in mainstream smoke of cigarettes, the reduction rate of the crotonaldehyde can reach 22.03-32.48%, and the reduction rate of the HCN can reach 21.58-34.20%; the patent CN106263024A prepares a tobacco additive, which can reduce 28.34% of phenol in smoke; the above patents have problems that the preparation process is complicated or it is difficult to remove various harmful substances at the same time. The method has great significance on reducing the release amount of phenol, HCN and crotonaldehyde and reducing the harm of smoking to health.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an adsorbing material capable of simultaneously reducing the release amount of phenol, hydrocyanic acid and crotonaldehyde in cigarette smoke. The adsorption material is a molecular sieve, and is used for preparing the cigarette composite filter tip, so that the release amount of phenol, hydrocyanic acid and crotonaldehyde in cigarette smoke is reduced; the invention also provides a preparation method of the adsorption material, the adsorption material is prepared by a hydrothermal synthesis method, the APO-5 molecular sieve is modified by adopting a lattice substitution method, the electronegativity of FeAPO-5 is changed after Fe is added, and a B acid site center is generated, after the material is used for preparing a composite filter tip in a cigarette filter tip, the release amount of phenol, HCN and crotonaldehyde in mainstream smoke of the cigarette can be effectively reduced, and the release amount can be reduced to the maximum extent: 58 percent, 55 percent and 54 percent, thereby having better popularization and application values.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a modified phosphorus-aluminum molecular sieve filter tip adsorption material comprises the following steps:
step (1), preparation of FeAPO-5 initial gel: preparing pseudo-boehmite into suspension by using water, dissolving ferric nitrate by using water, adding the dissolved ferric nitrate into the pseudo-boehmite suspension, and stirring and mixing the mixture until the mixture is in a suspension state; then, dropwise adding phosphoric acid with the volume concentration of 80-85% under the stirring state, continuously stirring for 0.9-1.1 h after the addition is finished, dropwise adding triethylamine under the stirring state, and continuously stirring for 1.9-2.1 h after the addition is finished to obtain FeAPO-5 initial gel;
wherein, the iron nitrate and Al in the pseudo-boehmite2O3、H3PO4And the molar ratio of the total dosage of triethylamine and water is n: (1-n): 1: 0.74-0.76: m, wherein n = 0.03-0.09, m = 1.00-1.22;
the total amount of the water is the sum of the amount of crystal water contained in the pseudo-boehmite, the amount of water used for preparing the pseudo-boehmite into a suspension and the amount of water used for dissolving ferric nitrate;
step (2), crystallizing, drying and roasting: adding the FeAPO-5 initial gel prepared in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at the temperature of 180-200 ℃ for 24-48 h, taking out, rapidly cooling to room temperature, washing with water for 2-5 times, drying in an oven at the temperature of 118-122 ℃ for 7.5-8.5 h, taking out, grinding into fine powder of minus 100 meshes, and roasting the fine powder in a muffle furnace at the temperature of 450-650 ℃ for 4-6 h to obtain FeAPO-5, namely the modified phosphorus-aluminum molecular sieve filter adsorbing material.
Further, in the step (1), it is preferable that the water used for the pseudo-boehmite and the water used for the dissolution of the iron nitrate are both distilled water.
Further, it is preferable that, after crystallization in step (2), the crystal is taken out and cooled with ice water to be rapidly cooled to room temperature.
Further, in the step (2), it is preferable that deionized water is used for washing in the step (2).
The amount of water used in the washing of the present invention is not particularly limited, and may be carried out according to a conventional technique in the art.
Further, in the step (2), it is preferable that an agate mortar is used when the powder is ground into fine powder.
The invention also provides a modified phosphorus-aluminum molecular sieve filter tip adsorption material prepared by the preparation method of the modified phosphorus-aluminum molecular sieve filter tip adsorption material.
The invention also provides application of the modified phosphorus-aluminum molecular sieve filter tip adsorption material prepared by the preparation method of the modified phosphorus-aluminum molecular sieve filter tip adsorption material as a cigarette additive.
Further, it is preferable that the modified aluminophosphate molecular sieve filter adsorption material is added to a cigarette filter.
Further, it is preferable that the amount added is 20 mg/liter.
The amount of crystal water contained in the pseudoboehmite, the amount of water used for making the pseudoboehmite into a suspension, and the amount of water used for dissolving the ferric nitrate in the present invention are not particularly limited as long as the total amount is within the range defined in the present invention.
Compared with the prior art, the invention has the beneficial effects that:
(1) the prepared FeAPO-5 is granulated and added to the middle part of the cigarette filter according to the addition amount of 20 mg/cigarette, so that the effect of reducing the release amount of phenol, HCN and crotonaldehyde in cigarette smoke is better, and no molecular sieve component is found in the Cambridge filter sheet after infrared test adsorption, which indicates that the material has good safety.
(2) The invention provides a preparation method of a modified phosphorus-aluminum molecular sieve filter tip adsorption material, belonging to a hydrothermal synthesis method, wherein the prepared adsorption material is a mesoporous APO-5 molecular sieve with uniform aperture, and the iron load of Fe atoms entering an APO-5 framework is a lattice substitution load, namely, aluminum-oxygen tetrahedron in the framework is replaced by coordination tetrahedron of partial iron metal and oxygen generated in the molecular sieve framework.
(3) The invention adopts a lattice substitution method to modify the APO-5 molecular sieve, FeAPO-5 changes electronegativity after Fe is added to generate a B acid site center, and after the material is used for preparing a composite filter tip in a cigarette filter tip, the release amount of phenol, HCN and crotonaldehyde in mainstream smoke of the cigarette can be effectively reduced, and the release amount can be reduced to the maximum extent: 58 percent, 55 percent and 54 percent, thereby having better popularization and application values.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image at 20 μm of a modified aluminum phosphate molecular sieve prepared according to example nine of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image at 10 μm of a modified aluminum phosphate molecular sieve prepared according to example nine of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available by purchase.
Example 1
A preparation method of a modified phosphorus-aluminum molecular sieve filter tip adsorption material comprises the following steps:
step (1), preparation of FeAPO-5 initial gel: preparing pseudo-boehmite into suspension by using water, dissolving ferric nitrate by using water, adding the dissolved ferric nitrate into the pseudo-boehmite suspension, and stirring and mixing the mixture until the mixture is in a suspension state; then, dropwise adding phosphoric acid with volume concentration of 80% under a stirring state, continuously stirring for 0.9h after the addition is finished, dropwise adding triethylamine under a stirring state, and continuously stirring for 1.9h after the addition is finished to obtain FeAPO-5 initial gel;
wherein, the iron nitrate and Al in the pseudo-boehmite2O3、H3PO4The molar ratio of the total amount of triethylamine and water is 0.03: 0.97: 1: 0.75: 1.00;
the total amount of the water is the sum of the amount of crystal water contained in the pseudo-boehmite, the amount of water used for preparing the pseudo-boehmite into a suspension and the amount of water used for dissolving ferric nitrate;
step (2), crystallizing, drying and roasting: and (2) adding the FeAPO-5 initial gel prepared in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at the temperature of 200 ℃ for 36 hours, taking out, rapidly cooling the FeAPO-5 initial gel by using ice water at room temperature, washing for 2 times by using deionized water, drying in an oven at 118 ℃ for 7.5 hours, taking out, grinding the obtained product into fine powder with an agate mortar to minus 100 meshes, and roasting the fine powder in a muffle furnace at 550 ℃ for 6 hours to obtain the FeAPO-5, namely the modified phosphorus-aluminum molecular sieve filter tip adsorption material.
In the step (1), the water used for dissolving the pseudoboehmite and the water used for dissolving the ferric nitrate are distilled water.
Example 2
A preparation method of a modified phosphorus-aluminum molecular sieve filter tip adsorption material comprises the following steps:
step (1), preparation of FeAPO-5 initial gel: preparing pseudo-boehmite into suspension by using water, dissolving ferric nitrate by using water, adding the dissolved ferric nitrate into the pseudo-boehmite suspension, and stirring and mixing the mixture until the mixture is in a suspension state; then, dropwise adding phosphoric acid with volume concentration of 85% under a stirring state, continuously stirring for 1.1h after the addition is finished, dropwise adding triethylamine under a stirring state, and continuously stirring for 2.1h after the addition is finished to obtain FeAPO-5 initial gel;
wherein, the iron nitrate and Al in the pseudo-boehmite2O3、H3PO4The molar ratio of the total amount of triethylamine and water is 0.03: 0.97: 1: 0.75: 1.11;
the total amount of the water is the sum of the amount of crystal water contained in the pseudo-boehmite, the amount of water used for preparing the pseudo-boehmite into a suspension and the amount of water used for dissolving ferric nitrate;
step (2), crystallizing, drying and roasting: and (2) adding the FeAPO-5 initial gel prepared in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at the temperature of 180 ℃ for 24 hours, taking out, rapidly cooling the FeAPO-5 initial gel by using ice water at room temperature, washing for 5 times by using deionized water, drying in a drying oven at the temperature of 122 ℃ for 8.5 hours, taking out, grinding the FeAPO-5 initial gel into fine powder with an agate mortar to minus 100 meshes, and roasting the fine powder in a muffle furnace at the temperature of 450 ℃ for 5 hours to obtain the FeAPO-5, namely the modified phosphorus-aluminum molecular sieve filter adsorbing material.
In the step (1), the water used for dissolving the pseudoboehmite and the water used for dissolving the ferric nitrate are distilled water.
Example 3
A preparation method of a modified phosphorus-aluminum molecular sieve filter tip adsorption material comprises the following steps:
step (1), preparation of FeAPO-5 initial gel: preparing pseudo-boehmite into suspension by using water, dissolving ferric nitrate by using water, adding the dissolved ferric nitrate into the pseudo-boehmite suspension, and stirring and mixing the mixture until the mixture is in a suspension state; then, dropwise adding phosphoric acid with volume concentration of 80% under a stirring state, continuously stirring for 1h after the addition, dropwise adding triethylamine under a stirring state, and continuously stirring for 2h after the addition to obtain FeAPO-5 initial gel;
wherein, the iron nitrate and Al in the pseudo-boehmite2O3、H3PO4The molar ratio of the total amount of triethylamine and water is 0.03: 0.97: 1: 0.75: 1.22;
the total amount of the water is the sum of the amount of crystal water contained in the pseudo-boehmite, the amount of water used for preparing the pseudo-boehmite into a suspension and the amount of water used for dissolving ferric nitrate;
step (2), crystallizing, drying and roasting: adding the FeAPO-5 initial gel prepared in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at 190 ℃ for 48h, taking out, rapidly cooling the initial gel with ice water to room temperature, washing with deionized water for 2 times, drying in a 120 ℃ oven for 8h, taking out, grinding into fine powder with an agate mortar to minus 100 meshes, and roasting the fine powder in a 650 ℃ muffle furnace for 4h to obtain the FeAPO-5, namely the modified phosphorus-aluminum molecular sieve filter tip adsorbing material.
In the step (1), the water used for dissolving the pseudoboehmite and the water used for dissolving the ferric nitrate are distilled water.
Example 4
A preparation method of a modified phosphorus-aluminum molecular sieve filter tip adsorption material comprises the following steps:
step (1), preparation of FeAPO-5 initial gel: preparing pseudo-boehmite into suspension by using water, dissolving ferric nitrate by using water, adding the dissolved ferric nitrate into the pseudo-boehmite suspension, and stirring and mixing the mixture until the mixture is in a suspension state; then, dropwise adding phosphoric acid with volume concentration of 80% under a stirring state, continuously stirring for 0.9h after the addition is finished, dropwise adding triethylamine under a stirring state, and continuously stirring for 2.1h after the addition is finished to obtain FeAPO-5 initial gel;
wherein, the iron nitrate and Al in the pseudo-boehmite2O3、H3PO4The molar ratio of the total amount of triethylamine and water used was 0.06: 0.94: 1: 0.75: 1.00;
the total amount of the water is the sum of the amount of crystal water contained in the pseudo-boehmite, the amount of water used for preparing the pseudo-boehmite into a suspension and the amount of water used for dissolving ferric nitrate;
step (2), crystallizing, drying and roasting: and (2) adding the FeAPO-5 initial gel prepared in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at the temperature of 180 ℃ for 48 hours, taking out, rapidly cooling the FeAPO-5 initial gel by using ice water at room temperature, washing for 4 times by using deionized water, drying in a 119 ℃ oven for 7.6 hours, taking out, grinding the FeAPO-5 initial gel into fine powder with an agate mortar to minus 100 meshes, and roasting the fine powder in a 450 ℃ muffle furnace for 6 hours to obtain the FeAPO-5, namely the modified phosphorus-aluminum molecular sieve filter adsorbing material.
In the step (1), the water used for dissolving the pseudoboehmite and the water used for dissolving the ferric nitrate are distilled water.
Example 5
A preparation method of a modified phosphorus-aluminum molecular sieve filter tip adsorption material comprises the following steps:
step (1), preparation of FeAPO-5 initial gel: preparing pseudo-boehmite into suspension by using water, dissolving ferric nitrate by using water, adding the dissolved ferric nitrate into the pseudo-boehmite suspension, and stirring and mixing the mixture until the mixture is in a suspension state; then, dropwise adding 83% phosphoric acid in a stirring state, continuously stirring for 1 hour after the addition, dropwise adding triethylamine in a stirring state, and continuously stirring for 1.95 hours after the addition to obtain FeAPO-5 initial gel;
wherein, the iron nitrate and Al in the pseudo-boehmite2O3、H3PO4TriethylamineAnd water in a molar ratio of 0.06: 0.94: 1: 0.76: 1.22;
the total amount of the water is the sum of the amount of crystal water contained in the pseudo-boehmite, the amount of water used for preparing the pseudo-boehmite into a suspension and the amount of water used for dissolving ferric nitrate;
step (2), crystallizing, drying and roasting: adding the FeAPO-5 initial gel prepared in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at the temperature of 200 ℃ for 24 hours, taking out, rapidly cooling the initial gel by using ice water at room temperature, washing by using deionized water for 3 times, drying in a drying oven at 121 ℃ for 8 hours, taking out, grinding into fine powder with an agate mortar to minus 100 meshes, and roasting the fine powder in a muffle furnace at 550 ℃ for 4 hours to obtain the FeAPO-5, namely the modified phosphorus-aluminum molecular sieve filter tip adsorbing material.
In the step (1), the water used for dissolving the pseudoboehmite and the water used for dissolving the ferric nitrate are distilled water.
Example 6
A preparation method of a modified phosphorus-aluminum molecular sieve filter tip adsorption material comprises the following steps:
step (1), preparation of FeAPO-5 initial gel: preparing pseudo-boehmite into suspension by using water, dissolving ferric nitrate by using water, adding the dissolved ferric nitrate into the pseudo-boehmite suspension, and stirring and mixing the mixture until the mixture is in a suspension state; then, dropwise adding phosphoric acid with volume concentration of 80% under a stirring state, continuously stirring for 1h after the addition, dropwise adding triethylamine under a stirring state, and continuously stirring for 2h after the addition to obtain FeAPO-5 initial gel;
wherein, the iron nitrate and Al in the pseudo-boehmite2O3、H3PO4The molar ratio of the total amount of triethylamine and water used was 0.06: 0.94: 1: 0.74: 1.22;
the total amount of the water is the sum of the amount of crystal water contained in the pseudo-boehmite, the amount of water used for preparing the pseudo-boehmite into a suspension and the amount of water used for dissolving ferric nitrate;
step (2), crystallizing, drying and roasting: adding the FeAPO-5 initial gel prepared in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at 190 ℃ for 36 hours, taking out, rapidly cooling the initial gel with ice water to room temperature, washing with deionized water for 3 times, drying in a 120 ℃ oven for 8 hours, taking out, grinding into fine powder with an agate mortar to minus 100 meshes, and roasting the fine powder in a 450 ℃ muffle furnace for 6 hours to obtain the FeAPO-5, namely the modified phosphorus-aluminum molecular sieve filter tip adsorbing material.
In the step (1), the water used for dissolving the pseudoboehmite and the water used for dissolving the ferric nitrate are distilled water.
Example 7
A preparation method of a modified phosphorus-aluminum molecular sieve filter tip adsorption material comprises the following steps:
step (1), preparation of FeAPO-5 initial gel: preparing pseudo-boehmite into suspension by using water, dissolving ferric nitrate by using water, adding the dissolved ferric nitrate into the pseudo-boehmite suspension, and stirring and mixing the mixture until the mixture is in a suspension state; then, dropwise adding phosphoric acid with volume concentration of 85% under the stirring state, continuously stirring for 1.05h after the addition is finished, dropwise adding triethylamine under the stirring state, and continuously stirring for 2.05h after the addition is finished to obtain FeAPO-5 initial gel;
wherein, the iron nitrate and Al in the pseudo-boehmite2O3、H3PO4The molar ratio of the total amount of triethylamine and water used was 0.09: 0.91: 1: 0.75: 1.00;
the total amount of the water is the sum of the amount of crystal water contained in the pseudo-boehmite, the amount of water used for preparing the pseudo-boehmite into a suspension and the amount of water used for dissolving ferric nitrate;
step (2), crystallizing, drying and roasting: and (2) adding the FeAPO-5 initial gel prepared in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at 190 ℃ for 24 hours, taking out, rapidly cooling the FeAPO-5 initial gel by using ice water at room temperature, washing for 4 times by using deionized water, drying in a drying oven at 121 ℃ for 8.2 hours, taking out, grinding into fine powder with an agate mortar to minus 100 meshes, and roasting the fine powder in a muffle furnace at 450 ℃ for 4 hours to obtain the FeAPO-5, namely the modified phosphorus-aluminum molecular sieve filter tip adsorbing material.
In the step (1), the water used for dissolving the pseudoboehmite and the water used for dissolving the ferric nitrate are distilled water.
Example 8
A preparation method of a modified phosphorus-aluminum molecular sieve filter tip adsorption material comprises the following steps:
step (1), preparation of FeAPO-5 initial gel: preparing pseudo-boehmite into suspension by using water, dissolving ferric nitrate by using water, adding the dissolved ferric nitrate into the pseudo-boehmite suspension, and stirring and mixing the mixture until the mixture is in a suspension state; then, dropwise adding phosphoric acid with volume concentration of 85% under a stirring state, continuously stirring for 1h after the addition, dropwise adding triethylamine under a stirring state, and continuously stirring for 2h after the addition to obtain FeAPO-5 initial gel;
wherein, the iron nitrate and Al in the pseudo-boehmite2O3、H3PO4The molar ratio of the total amount of triethylamine and water used was 0.09: 0.91: 1: 0.75: 1.11;
the total amount of the water is the sum of the amount of crystal water contained in the pseudo-boehmite, the amount of water used for preparing the pseudo-boehmite into a suspension and the amount of water used for dissolving ferric nitrate;
step (2), crystallizing, drying and roasting: adding the FeAPO-5 initial gel prepared in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at the temperature of 200 ℃ for 48 hours, taking out, rapidly cooling the initial gel by using ice water at room temperature, washing for 3 times by using deionized water, drying in a 120 ℃ oven for 8 hours, taking out, grinding the initial gel into fine powder with an agate mortar to minus 100 meshes, and roasting the fine powder in a 650 ℃ muffle furnace for 6 hours to obtain the FeAPO-5, namely the modified phosphorus-aluminum molecular sieve filter tip adsorbing material.
In the step (1), the water used for dissolving the pseudoboehmite and the water used for dissolving the ferric nitrate are distilled water.
Example 9
A preparation method of a modified phosphorus-aluminum molecular sieve filter tip adsorption material comprises the following steps:
step (1), preparation of FeAPO-5 initial gel: preparing pseudo-boehmite into suspension by using water, dissolving ferric nitrate by using water, adding the dissolved ferric nitrate into the pseudo-boehmite suspension, and stirring and mixing the mixture until the mixture is in a suspension state; then, dropwise adding phosphoric acid with volume concentration of 85% under a stirring state, continuously stirring for 1h after the addition, dropwise adding triethylamine under a stirring state, and continuously stirring for 2h after the addition to obtain FeAPO-5 initial gel;
wherein, the iron nitrate and Al in the pseudo-boehmite2O3、H3PO4The molar ratio of the total amount of triethylamine and water used was 0.09: 0.91: 1: 0.75: 1.22;
the total amount of the water is the sum of the amount of crystal water contained in the pseudo-boehmite, the amount of water used for preparing the pseudo-boehmite into a suspension and the amount of water used for dissolving ferric nitrate;
step (2), crystallizing, drying and roasting: adding the FeAPO-5 initial gel prepared in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at 180 ℃ for 36 hours, taking out, rapidly cooling the FeAPO-5 initial gel with ice water to room temperature, washing with deionized water for 3 times, drying in a 120 ℃ oven for 8 hours, taking out, grinding into fine powder with an agate mortar to minus 100 meshes, roasting the fine powder in a 550 ℃ muffle furnace for 5 hours to obtain the FeAPO-5, namely the modified phosphorus-aluminum molecular sieve filter tip adsorbing material, wherein a scanning electron microscope image of the FeAPO-5 is shown in FIGS. 1 and 2.
In the step (1), the water used for dissolving the pseudoboehmite and the water used for dissolving the ferric nitrate are distilled water.
Application method
The acetate fiber filter of the cigarette is cut from the middle part, the adsorbing materials prepared in the examples 1-9 are added into the acetate fiber filter, the adsorbing materials are granulated by a common granulator before being added, the particle size is controlled to be 40-60 meshes, the adsorbing materials are added into the cigarette filter by a normal activated carbon filter rod adding method, the adding amount is 20 mg/cigarette, blank cigarettes with the middle part of the filter cut but not added with FeAPO-5 are used as a control, 6 cigarettes are tested for each sample, a group of parallel samples are arranged, and smoke components are collected by 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, and the content of phenol, HCN and crotonaldehyde in the cigarette smoke passing through the filter is respectively measured by a straight-line smoking machine of CERULEANSM450 type of British Silvestre according to the method specified in GB/T19609-2004, and the result is shown in Table 1.
TABLE 1 test results of phenol, HCN and crotonaldehyde content in cigarette smoke after passing through filter
From the detection results in the table, the release amounts of phenol, HCN and crotonaldehyde in smoke can be well reduced after the adsorbing material prepared by the invention is added into a cigarette filter. When the preparation conditions are as follows: the prepared Fe-APO5 molecular sieve can achieve the best adsorption effect when the metal molar ratio (Fe: Al) is 0.09, the crystallization time is 36h, the crystallization temperature is 180 ℃, the demolding time is 5h, and the demolding temperature is 550 ℃, and the reduction rates of phenol, HCN and crotonaldehyde in the smoke respectively reach 58%, 55% and 54%.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A cigarette filter for reducing the release amount of phenol, HCN and crotonaldehyde in mainstream smoke of cigarettes is characterized in that: the cigarette filter contains a modified phosphorus-aluminum molecular sieve filter adsorbing material;
the preparation method of the modified phosphorus-aluminum molecular sieve filter tip adsorption material comprises the following steps:
step (1), preparation of FeAPO-5 initial gel: preparing pseudo-boehmite into suspension by using water, dissolving ferric nitrate by using water, adding the dissolved ferric nitrate into the pseudo-boehmite suspension, and stirring and mixing the mixture until the mixture is in a suspension state; then, dropwise adding phosphoric acid with the volume concentration of 80-85% under the stirring state, continuously stirring for 0.9-1.1 h after the addition is finished, dropwise adding triethylamine under the stirring state, and continuously stirring for 1.9-2.1 h after the addition is finished to obtain FeAPO-5 initial gel;
wherein, the iron nitrate and Al in the pseudo-boehmite2O3、H3PO4And the molar ratio of the total dosage of triethylamine and water is n: (1-n): 1: 0.74-0.76: m, wherein n = 0.03-0.09, m = 1.00-1.22;
the total amount of the water is the sum of the amount of crystal water contained in the pseudo-boehmite, the amount of water used for preparing the pseudo-boehmite into a suspension and the amount of water used for dissolving ferric nitrate;
step (2), crystallizing, drying and roasting: adding the FeAPO-5 initial gel prepared in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at the temperature of 180-200 ℃ for 24-48 h, taking out, rapidly cooling to room temperature, then washing with water for 2-5 times, drying in an oven at the temperature of 118-122 ℃ for 7.5-8.5 h, taking out, grinding into fine powder of minus 100 meshes, and finally roasting the fine powder in a muffle furnace at the temperature of 450-650 ℃ for 4-6 h to obtain FeAPO-5, namely the modified phosphorus-aluminum molecular sieve filter tip adsorption material;
in the step (2), after crystallization, taking out and cooling the crystal by using ice water to quickly cool the crystal to room temperature;
in the step (1), the water used for preparing the pseudoboehmite into the suspension and the water used for dissolving the ferric nitrate are distilled water;
in the step (2), deionized water is adopted for washing during water washing.
2. The cigarette filter for reducing the release of phenol, HCN and crotonaldehyde in mainstream smoke of cigarettes according to claim 1, wherein in the step (2), the fine powder is ground into fine powder by using an agate mortar.
3. The cigarette filter for reducing the release amount of phenol, HCN and crotonaldehyde in mainstream smoke of cigarettes according to claim 1, wherein the modified aluminophosphate molecular sieve filter adsorbing material is added into the cigarette filter in an amount of 20 mg/filter.
4. The modified aluminophosphate molecular sieve filter adsorbent material prepared in the cigarette filter for reducing the release amount of phenol, HCN and crotonaldehyde in mainstream smoke of cigarettes according to any one of claims 1 to 3.
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| CN107934983A (en) * | 2017-12-13 | 2018-04-20 | 重庆中烟工业有限责任公司 | Micro- mesoporous yolk shell composite molecular sieve of a kind of carried metal and preparation method thereof and a kind of cigarette |
| CN108033457A (en) * | 2017-12-13 | 2018-05-15 | 重庆中烟工业有限责任公司 | A kind of micro- mesoporous yolk-shell composite molecular sieve and preparation method thereof and a kind of cigarette |
| CN108187603A (en) * | 2018-01-03 | 2018-06-22 | 昆明理工大学 | A kind of modified phosphate aluminum molecular screen material and preparation method and application |
| CN108272133A (en) * | 2018-01-03 | 2018-07-13 | 昆明理工大学 | A kind of additive and the preparation method and application thereof |
| CN108246247A (en) * | 2018-01-03 | 2018-07-06 | 昆明理工大学 | A kind of modified phosphate aluminum molecular screen flue gas sorbing material and preparation method and application |
| CN108246248A (en) * | 2018-01-03 | 2018-07-06 | 昆明理工大学 | A kind of additive of selective absorption crotonaldehyde and phenol and preparation method and application |
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| CN102205975A (en) * | 2011-05-28 | 2011-10-05 | 山西昆明烟草有限责任公司 | Modified aluminium phosphate molecular sieve additive capable of reducing aldehyde and ketone compound contents in cigarette smoke as well as preparation and application thereof |
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| CN1708241A (en) * | 2002-10-31 | 2005-12-14 | 菲利普莫里斯生产公司 | Electrically heated cigarette including controlled-release flavoring |
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