Preparation method of CuNPS-(ZSM-5) molecular sieve antibacterial material and anti-deterioration treatment method of tobacco charging essence

Abstract

The invention discloses a preparation method of a CuNPS-(ZSM-5) molecular sieve antibacterial material and an anti-deterioration treatment method of tobacco charging essence, and the preparation method of the CuNPS-(ZSM-5) molecular sieve antibacterial material comprises the following steps: dispersing ZSM-5 in a toluene solution, adding a certain mass of n-octyltriethoxysilane, placing in an oil bath at 130-160 DEG C, and condensing and refluxing for 20-24 hours; carrying out suction filtration and toluene washing; performing vacuum drying to obtain pretreated ZSM-5; under magnetic stirring, slowly dissolving Arabic gum in distilled water, adding the pretreated ZSM-5 molecular sieve, stirring for 30 minutes, dropwise adding a copper sulfate solution, continuously stirring for 30 minutes, adding a hydrazine hydrate solution, continuously stirring for 1 hour, filtering, washing with 95% ethanol, and performing vacuum drying to obtain the CuNPS-(ZSM-5) molecular sieve antibacterial material. The CuNPS-(ZSM-5) molecular sieve antibacterial material provided by the invention can be used for quickly sterilizing the tobacco flavoring essence, so that the shelf life of the flavoring essence is prolonged, and the quality stability of the flavoring essence is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of tobacco, and in particular to a CuNP S -(ZSM-5) molecular sieve antibacterial material preparation and tobacco flavoring anti-deterioration treatment method. Background Art

[0002] Nano copper refers to single copper particles with a particle size of less than 100 nm prepared by certain chemical or physical methods. It has a series of advantages such as broad-spectrum antibacterial, high temperature resistance, and strong durability. It is widely used in various fields such as food and medicine. Compared with silver nanoparticles, copper nanoparticles have higher electrical conductivity and thermal conductivity, and lower cost, and are a good substitute for silver. However, due to its small particle size and large specific surface area, CuNPs can easily hinder the dispersion of nanopowders and cause them to agglomerate, and cannot exert good antibacterial activity. Therefore, it is necessary to compound nano copper with a variety of antibacterial agents and carriers through physical adsorption or chemical grafting to improve its dispersibility.

[0003] Tobacco flavoring mainly uses water as solvent system, and its main components are invert sugar and natural extracts. It is easy to undergo microbial fermentation, mildew, bubbles and other deterioration phenomena, which has become a potential threat to the stability of cigarette products. Molecular sieve is a kind of aluminosilicate compound with cubic lattice, which has a uniform microporous structure and uniform pore diameter. These pores can adsorb molecules smaller than its diameter into the cavity, and have preferential adsorption capacity for polar molecules and unsaturated molecules. Flavoring is a heat-sensitive product. Excessive temperature will change the color and flavor of flavoring. Therefore, non-heating sterilization technology / low-temperature long-time cold sterilization technology is used to ensure product quality without changing product flavor.

[0004] Therefore, the present invention aims to solve the problem that copper nanoparticles are prone to spontaneously aggregate into large particles, which affects their antibacterial properties. S -(ZSM-5) molecular sieve antibacterial material and its preparation method, and use the antibacterial material to quickly sterilize the added flavors to extend the shelf life of the added flavors and improve the quality stability of the added flavors. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a CuNP S -(ZSM-5) molecular sieve antibacterial material preparation and tobacco flavoring anti-deterioration treatment method, and apply it to tobacco flavoring for sterilization treatment, with the characteristics of simple operation, high efficiency and green, and can be repeatedly used, and the quality of the flavoring remains unchanged and stable after treatment.

[0006] The technical problem to be solved by the present invention is achieved through the following technical solutions:

[0007] A CuNP S -(ZSM-5) molecular sieve antibacterial material preparation method, comprising the following steps:

[0008] (1) Pretreatment of ZSM-5 molecular sieve: Disperse ZSM-5 in toluene solution, add a certain amount of n-octyltriethoxysilane, place in an oil bath at 130-160°C for condensation and reflux for 20-24 hours; filter and wash with toluene; vacuum dry to obtain pretreated ZSM-5;

[0009] (2) CuNP S -(ZSM-5) molecular sieve antibacterial material preparation: Gum arabic was slowly dissolved in distilled water under magnetic stirring, and the pretreated ZSM-5 molecular sieve was added. After stirring for 30 minutes, copper sulfate solution was added dropwise and continued to stir for 30 minutes. Hydrazine hydrate solution was added and continued to stir for 1 hour. After that, it was filtered and washed with 95% ethanol and dried in vacuum to obtain CuNP. S -(ZSM-5) molecular sieve antibacterial material.

[0010] Preferably, in the above technical solution, in step (1), the mass ratio of n-octyltriethoxysilane to ZSM-5 molecular sieve is 1:(20-30).

[0011] Preferably, in the above technical solution, in step (2), the concentration of gum arabic is controlled at 30% to 40%.

[0012] Preferably, in the above technical solution, in step (2), the molar ratio of copper sulfate to hydrazine hydrate solution is 1:(2-3).

[0013] Preferably, in the above technical solution, in step (2), the mass ratio of copper sulfate to pretreated ZSM-5 is 1:(10-15).

[0014] A CuNP S -(ZSM-5) molecular sieve antibacterial material, the CuNP S -(ZSM-5) molecular sieve antibacterial material is prepared according to the above preparation method.

[0015] A method using the CuNP S -(ZSM-5) molecular sieve antibacterial material to prevent deterioration of tobacco flavoring essence, comprising the following steps:

[0016] S1, CuNP S -(ZSM-5) molecular sieve antibacterial material is filled into a self-made filter ball box and the filter ball box is placed at the bottom of the flavoring stirring kettle;

[0017] S2. Prepare the added flavor according to the formula requirements of the cigarette flavor and fragrance product, pour the prepared added flavor into the stirring kettle and continue stirring for 30 minutes;

[0018] S3. After stirring is completed, open the discharge valve at the bottom of the stirring kettle, add the flavoring agent into the product packaging barrel, and seal it for storage.

[0019] A method according to the CuNP S -Application of (ZSM-5) molecular sieve antibacterial material in preventing tobacco flavoring from spoiling.

[0020] The above technical solution of the present invention has the following beneficial effects:

[0021] The CuNPs provided in this application S -(ZSM-5) molecular sieve antibacterial material has a simple preparation method. This material can quickly sterilize tobacco flavors to extend the shelf life of flavors and improve the quality stability of flavors. It is also highly efficient, green and reusable. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.

[0023] Figure 1 CuNP for this application S -Schematic diagram of the usage status of (ZSM-5) molecular sieve antibacterial material. DETAILED DESCRIPTION

[0024] Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that the relative arrangement of components and steps, numerical expressions and numerical values ​​set forth in these embodiments do not limit the scope of the present invention unless otherwise specifically stated.

[0025] Unless otherwise specified, the reagents used in this application are all commercially available or obtained through commercial channels, or can be prepared by referring to existing chemical methods.

[0026] Example 1

[0027] A CuNP S -(ZSM-5) molecular sieve antibacterial material preparation method, comprising the following steps:

[0028] (1) ZSM-5 molecular sieve pretreatment:

[0029] Disperse ZSM-5 in toluene solution, add a certain mass of n-octyltriethoxysilane, the mass ratio of n-octyltriethoxysilane to ZSM-5 molecular sieve is 1:20; place in a 130°C oil bath for condensation and reflux for 20 hours; filter and wash with toluene; and vacuum dry to obtain the pretreated ZSM-5.

[0030] (2) CuNP S -(ZSM-5) molecular sieve antibacterial material preparation:

[0031] Under magnetic stirring, gum arabic was slowly dissolved in distilled water, the concentration of gum arabic was controlled at 30%, the pretreated ZSM-5 molecular sieve was added, and after stirring for 30 minutes, copper sulfate solution was added dropwise and continued to stir for 30 minutes, hydrazine hydrate solution was added, and the molar ratio of copper sulfate to hydrazine hydrate solution was 1:2. After stirring for 1 hour, it was filtered and washed with 95% ethanol, and vacuum dried to obtain CuNP S -(ZSM-5) molecular sieve, the mass ratio of copper sulfate to pretreated ZSM-5 is 1:10.

[0032] Sterilization treatment in tobacco flavoring (anti-deterioration treatment method):

[0033] S1, CuNP S -(ZSM-5) molecular sieve antibacterial material is filled into a homemade filter ball box and the filter ball box is placed at the bottom of the flavoring stirring kettle (such as Figure 1 );

[0034] S2. Prepare the Red Flag Canal (mango) flavoring essence (provided by Henan China Tobacco Zhumadian Cigarette Factory) according to the formula requirements of cigarette flavors and fragrances, and pour the prepared flavoring essence into the stirring kettle and continue stirring for 30 minutes;

[0035] S3. After the stirring is completed, open the discharge valve at the bottom of the stirring kettle, pour the added flavor into the product packaging barrel, and seal it for storage. Take a sample and mark it as added flavor 1#.

[0036] Example 2

[0037] A CuNP S -(ZSM-5) molecular sieve antibacterial material preparation method, comprising the following steps:

[0038] (1) ZSM-5 molecular sieve pretreatment:

[0039] Disperse ZSM-5 in toluene solution, add a certain mass of n-octyltriethoxysilane, the mass ratio of n-octyltriethoxysilane to ZSM-5 molecular sieve is 1:30, place in a 160°C oil bath for condensation and reflux for 24 hours; filter and wash with toluene; and vacuum dry to obtain the pretreated ZSM-5.

[0040] (2) CuNP S -(ZSM-5) molecular sieve antibacterial material preparation:

[0041] Under magnetic stirring, gum arabic was slowly dissolved in distilled water, the concentration of gum arabic was controlled at 40%, the pretreated ZSM-5 molecular sieve was added, and after stirring for 30 minutes, copper sulfate solution was added dropwise and continued to stir for 30 minutes, and hydrazine hydrate solution was added, the molar ratio of copper sulfate to hydrazine hydrate solution was 1:3, and after continuing to stir for 1 hour, it was filtered and washed with 95% ethanol, and vacuum dried to obtain CuNP S -(ZSM-5) molecular sieve, the mass ratio of copper sulfate to pretreated ZSM-5 is 1:15.

[0042] Sterilization treatment in tobacco flavoring (anti-deterioration treatment method):

[0043] S1, CuNP S -(ZSM-5) molecular sieve antibacterial material is filled into a homemade filter ball box and the filter ball box is placed at the bottom of the flavoring stirring kettle (such as Figure 1 );

[0044] S2. Prepare the Red Flag Canal (mango) flavoring essence (provided by Henan China Tobacco Zhumadian Cigarette Factory) according to the formula requirements of cigarette flavors and fragrances, and pour the prepared flavoring essence into the stirring kettle and continue stirring for 30 minutes;

[0045] S3. After the stirring is completed, open the discharge valve at the bottom of the stirring kettle, pour the added flavor into the product packaging barrel, and seal it for storage. Take a sample and mark it as added flavor 2#.

[0046] Example 3

[0047] A CuNP S -(ZSM-5) molecular sieve antibacterial material preparation method, comprising the following steps:

[0048] (1) ZSM-5 molecular sieve pretreatment:

[0049] Disperse ZSM-5 in toluene solution, add a certain mass of n-octyltriethoxysilane, the mass ratio of n-octyltriethoxysilane to ZSM-5 molecular sieve is 1:25, place in a 150°C oil bath for condensation and reflux for 22 hours; filter and wash with toluene; and vacuum dry to obtain the pretreated ZSM-5.

[0050] (2) CuNP S -(ZSM-5) molecular sieve antibacterial material preparation:

[0051] Under magnetic stirring, gum arabic was slowly dissolved in distilled water, the concentration of gum arabic was controlled at 30%, the pretreated ZSM-5 molecular sieve was added, and after stirring for 30 minutes, copper sulfate solution was added dropwise and continued to stir for 30 minutes, and hydrazine hydrate solution was added, the molar ratio of copper sulfate to hydrazine hydrate solution was 1:3, and after continuing to stir for 1 hour, it was filtered and washed with 95% ethanol, and vacuum dried to obtain CuNP S -(ZSM-5) molecular sieve, the mass ratio of copper sulfate to pretreated ZSM-5 is 1:10.

[0052] Sterilization treatment in tobacco flavoring (anti-deterioration treatment method):

[0053] S1, CuNP S -(ZSM-5) molecular sieve antibacterial material is filled into a homemade filter ball box and the filter ball box is placed at the bottom of the flavoring stirring kettle (such as Figure 1 );

[0054] S2. Prepare the Red Flag Canal (mango) flavoring essence (provided by Henan China Tobacco Zhumadian Cigarette Factory) according to the formula requirements of cigarette flavors and fragrances, and pour the prepared flavoring essence into the stirring kettle and continue stirring for 30 minutes;

[0055] S3. After the stirring is completed, open the discharge valve at the bottom of the stirring kettle, pour the added flavor into the product packaging barrel, and seal it for storage. Take a sample and mark it as added flavor 3#.

[0056] Of course, the added flavors of the present application may also adopt the flavor and fragrance formula of the heated cigarette formula commonly used in the art, and are not limited to the above-mentioned products. The present application only uses this as an example for experimental explanation.

[0057] The added flavors prepared in Examples 1 to 3 were added to the cigarette shreds by spraying at a ratio of 2.65wt% in the adding process, and were recorded as cigarettes 1#, 2# and 3#; at the same time, the shredded tobacco added with the control sample added with flavors and fragrances was used as a blank control group, recorded as the control sample; cigarette products were made by conventional methods in the art, and the moisture was balanced (humidity 60%±2%, temperature 25±1°C) for 24h, and then sensory evaluation was carried out according to "YC / T 415-2011 Sensory Evaluation Method for Tobacco Products", and the results are shown in Table 1.

[0058] Table 1 Results of sensory quality evaluation of cigarettes

[0059]

[0060]

[0061] It can be seen from the evaluation results in Table 1 that the present invention is S-When the flavoring treated with (ZSM-5) molecular sieve antibacterial material is added to cigarettes, the aroma quality of the cigarettes is slightly improved, the irritation is slightly increased, and other indicators remain unchanged, indicating that the intrinsic quality of the flavoring after treatment has not changed and the product quality is stable.

[0062] The added flavors prepared in Examples 1 to 3 and the untreated control samples were placed in a constant temperature and humidity chamber, and the changes of the four samples over the storage time were observed. The results are shown in Table 2.

[0063] Table 2 Changes of added flavors

[0064] Storage time Control Additive flavor 1# Additive flavor 2# Additive flavor 3# Storage 5 days normal normal normal normal Storage for 10 days normal normal normal normal Storage 15 days Slight fermentation normal normal normal Storage for 30 days Rancidity normal normal normal Storage for 60 days Severe rancidity normal normal normal Storage for 90 days corruption Slight fermentation normal Slight fermentation

[0065] It can be seen from Table 2 that the CuNP S -(ZSM-5) molecular sieve antibacterial material treated flavoring has a much longer shelf life than untreated flavoring, thus improving product quality stability.

[0066] Although the present invention has been disclosed as above by the embodiments, it is not intended to limit the present invention. Any person skilled in the art may make various choices and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention is limited by the claims and their equivalents.

Claims

1. CuNP S -(ZSM-5) molecular sieve antibacterial material preparation method, characterized in that, The following steps are involved: (1) Pretreatment of ZSM-5 molecular sieve: Disperse ZSM-5 in toluene solution, add a certain amount of n-octyltriethoxysilane, place in an oil bath at 130-160°C for condensation and reflux for 20-24 hours; filter and wash with toluene; vacuum dry to obtain pretreated ZSM-5; (2) CuNP S -(ZSM-5) molecular sieve antibacterial material preparation: Gum arabic was slowly dissolved in distilled water under magnetic stirring, and the pretreated ZSM-5 molecular sieve was added. After stirring for 30 minutes, copper sulfate solution was added dropwise and continued to stir for 30 minutes. Hydrazine hydrate solution was added and continued to stir for 1 hour. After that, it was filtered and washed with 95% ethanol and dried in vacuum to obtain CuNP. S -(ZSM-5) molecular sieve antibacterial material.

2. CuNP according to claim 1 S -(ZSM-5) molecular sieve antibacterial material preparation method, characterized in that, In step (1), the mass ratio of n-octyltriethoxysilane to ZSM-5 molecular sieve is 1:(20-30).

3. CuNP according to claim 1 S -(ZSM-5) molecular sieve antibacterial material preparation method, characterized in that, In step (2), gum arabic is slowly dissolved in distilled water, and the concentration of gum arabic is controlled at 30% to 40%.

4. CuNP according to claim 1 S -(ZSM-5) molecular sieve antibacterial material preparation method, characterized in that, In step (2), the molar ratio of copper sulfate to hydrazine hydrate solution is 1:(2-3).

5. CuNP according to claim 1 S -(ZSM-5) molecular sieve antibacterial material preparation method, characterized in that, In step (2), the mass ratio of copper sulfate to pretreated ZSM-5 is 1:(10-15).

6. CuNP S -(ZSM-5) molecular sieve antibacterial material, characterized in that, The CuNP S -(ZSM-5) molecular sieve antibacterial material is prepared according to any one of the preparation methods described in claims 1-5.

7. A method using the CuNP according to claim 6 S -(ZSM-5) molecular sieve antibacterial material to prevent deterioration of tobacco flavoring, characterized in that: The following steps are involved: S1, CuNP S -(ZSM-5) molecular sieve antibacterial material is filled into a self-made filter ball box and the filter ball box is placed at the bottom of the flavoring stirring kettle; S2. Prepare the added flavor according to the formula requirements of the cigarette flavor and fragrance product, pour the prepared added flavor into the stirring kettle and continue stirring for 30 minutes; S3. After stirring is completed, open the discharge valve at the bottom of the stirring kettle, add the flavoring agent into the product packaging barrel, and seal it for storage.

8. A CuNP according to claim 6 S -Application of (ZSM-5) molecular sieve antibacterial material in preventing tobacco flavoring from spoiling.

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