Photodegradable filter stick and preparation method thereof

Abstract

The invention relates to the technical field of cigarette production, in particular to a photodegradable filter stick and a preparation method thereof. A photodegradable filter stick comprises a filter stick body, a plasticizer, a photodegradable catalyst and a photosensitizer. The preparation method of the photodegradable filter stick comprises the following steps: mixing a photocatalyst and a plasticizer, spraying the mixture on the filter stick, immersing the filter stick in a photosensitizer solution, and drying to obtain the photodegradable filter stick. According to the light degradation filter stick, the light degradation speed of the filter stick is effectively increased, and white pollution caused by the diacetate fiber tow filter stick is effectively reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of cigarette production, and particularly relates to a photo-degradable filter rod and a preparation method thereof. Background Art

[0002] With the development of the times, people's awareness of environmental protection has been continuously enhanced. Since plastic products cannot be degraded in the natural environment, causing "white pollution", the use and production of non-degradable plastic products have been restricted globally. Currently, most of the existing cigarette filter filling materials are two-acetate fiber tow, which has the advantages of good interception efficiency, moderate draw resistance, good thermal stability, non-toxic, harmless and odorless, especially having a good filtering effect on harmful substances in cigarette smoke such as tar and carbon monoxide. However, it is difficult to degrade in the natural environment and has a certain harm to the environment. Therefore, at present, major cigarette companies are all conducting research on improving the degradation efficiency of two-acetate fiber.

[0003] Photo-degradable two-acetate fiber is a relatively popular research direction. Research shows that the degradation of two-acetate fiber filter tips under sunlight irradiation requires at least 1 - 2 years, and it takes even longer under conditions of lack of light. Therefore, it is very important to design a cigarette filter rod with good photo-degradation effect. Summary of the Invention

[0004] The purpose of the present invention is to obtain a photo-degradable cigarette filter rod.

[0005] The first aspect of the present invention provides a photo-degradable filter rod, comprising a filter rod, a plasticizer, a photo-degradation catalyst and a photosensitizer.

[0006] Preferably, the filter rod is selected from one or more of two-acetate fiber tow or propylene fiber tow filter rods.

[0007] Preferably, the photo-degradation catalyst is titanium dioxide.

[0008] Preferably, the photosensitizer is selected from one or more of sodium copper chlorophyllin, methylene blue, rose bengal or porphyrin. A photosensitizer is a substance that can be adsorbed on the surface of a semiconductor, and by using the strong absorption of dyes for visible light, the spectral response of the system is extended to the visible region, thereby enhancing the photocatalytic efficiency of the photocatalyst. Among them, sodium copper chlorophyllin is a non-toxic, harmless, edible and water-soluble photosensitizer.

[0009] Preferably, the photo-degradable filter rod further comprises a plasticizer.

[0010] A1) The mass ratio of the filter rod to the photo-degradation catalyst is (7:100000) to (15:100000);

[0011] A2) The mass ratio of the photosensitizer to the photocatalytic degradation catalyst is 1.00 to 100.00;

[0012] A3) The mass ratio of the photocatalyst to the plasticizer is (1:1000) to (1:100);

[0013] A4) The mass ratio of the plasticizer to the filter rod is (7:100) to (15:100).

[0014] Preferably, the titanium dioxide is selected from one or more of anatase type and P25. Although P25 titanium dioxide has strong photocatalytic activity, its photocatalytic efficiency is limited because it only has photocatalytic activity when irradiated by ultraviolet light.

[0015] The present invention provides a method for producing a photocatalytic degradation filter rod. By adding titanium dioxide as a photocatalyst and sodium copper chlorophyllin as a photosensitizer to the filter rod, a photocatalytic degradation catalyst that can be accelerated in degradation under light conditions is formed. The degradation process is as follows: The photosensitizer broadens the response spectrum of P25 titanium dioxide. Under light conditions, P25 titanium dioxide has photocatalytic degradation activity and adsorbs on the surface of the diacetate fiber tow. The diacetate fiber reacts with water in the air to break the acetyl groups in the diacetate fiber, thereby achieving degradation. The photocatalytic degradation filter rod containing a photosensitizer prepared by the present invention can effectively improve the degradation efficiency of the diacetate fiber filter rod while not affecting the filtration efficiency of the filter rod for harmful substances in the flue gas.

[0016] The second aspect of the present invention provides a method for preparing the above-mentioned photocatalytic degradation filter rod, which includes mixing a photocatalyst and a plasticizer and then spraying them on the filter rod. Then, the filter rod is immersed in a photosensitizer solution and dried to obtain the photocatalytic degradation filter rod.

[0017] Preferably, B1) during the mixing, a stirrer is used for the first stirring until a suspension state is reached;

[0018] Preferably, B2) before the spraying, the filter rod is loosened;

[0019] Preferably, B3) the solvent of the photosensitizer solution is selected from one or more of water, ethanol or acetone;

[0020] Preferably, B4) when preparing the photosensitizer solution, a stirrer is used for the second stirring;

[0021] Preferably, B5) the immersion time is 24 to 36 h, for example, it can be 24 to 26 h, 26 to 28 h, 28 to 30 h, 30 to 32 h, 32 to 34 h, 34 to 36 h, etc.

[0022] Preferably, in B6), when soaking, the number of filter rods soaked in every 1000 mL of photosensitizer solution is 200 - 400, for example, it can be 200 - 250, 250 - 300, 300 - 350, 350 - 400.

[0023] Preferably, in B7), the drying temperature is 40 - 50 °C, for example, it can be 40 - 42 °C, 42 - 44 °C, 44 - 46 °C, 46 - 48 °C, 48 - 50 °C, etc.

[0024] Preferably, in B8), the drying time is 24 - 36 h, for example, it can be 24 - 26 h, 26 - 28 h, 28 - 30 h, 30 - 32 h, 32 - 34 h, 34 - 36 h, etc.

[0025] Preferably, in B11), in feature B1), the rotation speed of the first stirring is 500 - 1000 r / min;

[0026] Preferably, in B12), in feature B1), the first stirring time is 20 - 45 min, for example, it can be 20 - 25 min, 25 - 30 min, 30 - 35 min, 35 - 40 min, 40 - 45 min, etc.

[0027] Preferably, in B31), in feature B3), the mass ratio of the photosensitizer to the solvent is (0.1:100) - (1:100);

[0029] Preferably, in B41), in feature B4), the rotation speed of the second stirring is 200 - 550 r / min, for example, it can be 200 - 250 r / min, 250 - 300 r / min, 300 - 350 r / min, 350 - 400 r / min, 400 - 450 r / min, 450 - 500 r / min, 500 - 550 r / min, etc.

[0030] Preferably, in B42), in feature B4), the second stirring time is 15 - 30 min, for example, it can be 15 - 17 min, 17 - 19 min, 19 - 21 min, 21 - 23 min, 23 - 25 min, 25 - 27 min, 27 - 30 min, etc.

[0031] The present invention has the following beneficial effects:

[0032] 1) The photo - degradable filter rod of the present invention effectively improves the photo - degradation speed of the filter rod and effectively reduces the white pollution caused by the two - acetate fiber tow filter rod.

[0033] 2) In the preparation method of the photo - degradable filter rod of the present invention, the addition method of the photosensitizer is simple and can be used for large - scale mass production;

[0034] 3) The preparation method of the photodegradable filter rod in the present invention is simple to operate. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is the degradation effect diagram of the sample of the present invention in the natural environment.

[0036] Figure 2 It is the infrared spectrum of the sample B2 of the example under light-proof storage and ultraviolet degradation conditions. DETAILED DESCRIPTION OF THE INVENTION

[0037] The following specific examples illustrate the implementation manners of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation manners. Various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0038] When the examples give numerical ranges, it should be understood that unless otherwise specified in the present invention, any value at both ends of each numerical range and any value between the two ends can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those skilled in the art in this technical field. In addition to the specific methods, devices, and materials used in the examples, according to the knowledge of those skilled in the art in the prior art and the description of the present invention, any methods, devices, and materials similar to or equivalent to those described in the examples of the present invention can also be used to implement the present invention.

[0039] COMPARATIVE EXAMPLE

[0040] A filter rod containing anatase diacetate fiber tow

[0041] The diacetate fiber tow involved in this comparative example is a diacetate fiber tow containing anatase as a brightening agent, wherein the content of anatase is 0.08% of the total mass of the diacetate fiber tow filter rod, and the content of glyceride is 10% of the total mass of the diacetate fiber tow filter rod.

[0042] The above diacetate fiber tow is opened and enters the cigarette rod for forming through a nozzle, and after being cut by a cutting device, the comparative example filter rod is obtained, denoted as sample A.

[0043] EXAMPLE 1

[0044] Preparation of a diacetate fiber tow filter rod added with P25

[0045] The diacetate fiber tow involved in this example does not contain titanium dioxide. The preparation of the diacetate fiber tow filter rod added with P25 includes the following steps:

[0046] Step 1: Preparation of P25-triacetin suspension

[0047] Add P25 titanium dioxide into the plasticizer triacetin, where the mass ratio of P25 titanium dioxide to glyceride is 0.8:100, and stir with a stirrer for 30 min to obtain the P25-triacetin suspension;

[0048] Step 2: Filter rod forming

[0049] Pour the above-mentioned P25-triacetin suspension into the glyceride application device; the diacetate fiber tow without titanium dioxide is loosened and then passes through the glyceride application device to apply the plasticizer P25-triacetin suspension. The application ratio of the plasticizer P25-triacetin suspension is 10% of the total mass of the filter rod. Further, the tow enters the cigarette rod for forming through a nozzle and is cut by a cutting device to obtain the filter rod of this example, denoted as sample B.

[0050] Example 2

[0051] Preparation of diacetate fiber tow filter rod added with photosensitizer and P25

[0052] Based on Example 1, this example adds sodium copper chlorophyllin with different concentrations as the photosensitizer. The specific addition steps are as follows:

[0053] Step 1: Preparation of sodium copper chlorophyllin solution

[0054] (1) 0.2% sodium copper chlorophyllin solution: Weigh 2.0 g of sodium copper chlorophyllin and dissolve it in 1000 mL of water, and stir for 30 min;

[0055] (2) 0.5% sodium copper chlorophyllin solution: Weigh 5.0 g of sodium copper chlorophyllin and dissolve it in 1000 mL of water, and stir for 30 min;

[0056] (3) 0.8% sodium copper chlorophyllin solution: Weigh 8.0 g of sodium copper chlorophyllin and dissolve it in 1000 mL of water, and stir for 30 min;

[0057] Step 2: Treatment by immersion method

[0058] Take 200 diacetate fiber tow filter rods containing photocatalyst in Example 1 and immerse them in 1000 mL of 0.2% sodium copper chlorophyllin solution for 24 hours, denoted as sample B1;

[0059] Take 200 diacetate fiber tow filter rods containing photocatalyst in Example 1 and immerse them in 1000 mL of 0.5% sodium copper chlorophyllin solution for 24 hours, denoted as sample B2;

[0060] Take 200 cellulose diacetate tow filters containing photocatalyst from Example 1, immerse them in 1000 mL of 0.8% sodium copper chlorophyllin solution for 24 hours, and label them as Sample B3;

[0061] Take 200 cellulose diacetate tow filters containing photocatalyst from the comparative example, immerse them in 1000 mL of 0.2% sodium copper chlorophyllin solution for 24 hours, and label them as Sample A1;

[0062] Take 200 cellulose diacetate tow filters containing photocatalyst from the comparative example, immerse them in 1000 mL of 0.5% sodium copper chlorophyllin solution for 24 hours, and label them as Sample A2;

[0063] Take 200 cellulose diacetate tow filters containing photocatalyst from the comparative example, immerse them in 1000 mL of 0.8% sodium copper chlorophyllin solution for 24 hours, and label them as Sample A3;

[0064] The third step is drying treatment

[0065] Take out the filters in the second step, place them in an oven at 45 °C, and dry for 36 hours to obtain dry cellulose diacetate tow filters added with photosensitizer and P25.

[0066] Evaluate the degradation performance of the above control example and the cellulose diacetate tow filters of Example 2. The specific evaluation method is as follows:

[0067] Select three conditions: soil environment, storage environment, and ultraviolet irradiation environment, and detect the degradation performance of the above Samples A, B, A1, A2, A3, B1, B2, and B3;

[0068] The evaluation standard for the filter degradation performance is: evaluate the filter degradation performance through the mass loss rate of the filter;

[0069] The calculation method of the mass loss rate is: M%=(m1 - m2) / m1

[0070] Where M% refers to the mass loss rate; m1 refers to the original mass of the filter; m2 refers to the existing mass of the filter;

[0071] The natural environment refers to placing the filter on the soil surface for 6 months of degradation time;

[0072] The ultraviolet environment refers to placing the filter under ultraviolet lamp irradiation for 7 days of degradation time;

[0073] The wavelength of the above ultraviolet lamp is 200 - 340 nm, and the power is 100 W;

[0074] The storage environment mentioned above refers to that the filter rods are stored in a filter rod box in the dark, the storage temperature is 25°C, and the degradation time is 6 months.

[0075] Table 1 Mass loss rate of filter rods degraded for 3 months under natural conditions

[0076] Sample A Sample A1 Sample A2 Sample A3 Sample B Sample B1 Sample B2 Sample B3 M％ 10.1 12.4 13.3 13.9 21.6 26.9 30.8 32.3

[0077] Table 2 Mass loss rate of filter rods degraded for 7 days under ultraviolet conditions

[0078] Sample A Sample A1 Sample A2 Sample A3 Sample B Sample B1 Sample B2 Sample B3 M％ 10.5 11.1 11.2 11.2 22.0 22.1 22.2 22.3

[0079] Table 3 Mass loss rate of filter rods degraded for 6 months under storage conditions

[0080] Sample A Sample A1 Sample A2 Sample A3 Sample B Sample B1 Sample B2 Sample B3 M％ 1.1 1.2 1.0 1.2 1.2 1.3 1.2 1.2

[0081] From Figure 1 it can be seen that in the natural environment, as time increases, the mass loss rate of the filter rods gradually increases. Among them, the degradation effect of the filter rods containing photosensitizer is better than that without photosensitizer; the degradation efficiency of the filter rods containing P25 is better than that of the filter rods containing anatase.

[0082] From the data in Table 3, it can be seen that under the condition of light-shielded storage, the degradation efficiencies of various samples are not very different; from the data in Table 1 and Table 2, it can be seen that P25 titanium dioxide has a better degradation effect on the filter rods; under the conditions of ultraviolet irradiation and storage, adding photosensitizer has no obvious effect on the degradation efficiency of the filter rods; under natural conditions, photosensitizer effectively improves the degradation efficiency of photocatalytic degradation of filter rods.

[0083] Example 4

[0084] Degradation mechanism of the degradable filter rods containing photosensitizer in the present invention

[0085] Infrared detection was carried out on sample B2 stored in the dark and sample B2 degraded for 7 days under ultraviolet conditions in the above examples. The infrared spectrogram is shown in Figure 2 .

[0086] There are four relatively strong absorption peaks of acetyl groups in diacetate fiber in the infrared spectrogram, which are 1757 cm -1 , 1388 cm -1 , 1239 cm -1 and 1023 cm -1 , respectively. Among them, 1757 cm -1 is the stretching vibration absorption of C=O, 1388 cm -1 is the characteristic absorption of methyl, 1239 cm -1 is the asymmetric stretching vibration absorption of C-O-C, and 1023 cm -1 is the rocking vibration of methyl. From Figure 2It can be seen that the infrared absorption peak of the acetyl group in sample B2 degraded under ultraviolet conditions has weakened, indicating a decrease in the number of acetyl groups; a new peak appears at 1589 cm -1 , and it is speculated that an enol structure is formed; the infrared absorption peak at 1640 cm -1 is strengthened. It is speculated that during the degradation process, after the photocatalysis of diacetate fiber, the adsorbed water interacting with it increases, indicating that water participates in the reaction during the photocatalysis process.

[0087] The above is only the preferred embodiment of the present invention, and it is not a limitation to the present invention in any form and essence. It should be pointed out that for those of ordinary skill in the art of this technology, without departing from the premise of the method of the present invention, several improvements and supplements can still be made, and these improvements and supplements should also be regarded as the protection scope of the present invention. Any equivalent changes in the form of slight changes, modifications and evolutions made by those who are familiar with the technology in this field without departing from the spirit and scope of the present invention by using the technical content disclosed above are all equivalent embodiments of the present invention; at the same time, any equivalent changes in the form of changes, modifications and evolutions made to the above embodiments according to the essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A photodegradable filter rod, characterized in that, It includes a filter rod, a plasticizer, a photocatalytic degradation catalyst and a photosensitizer.

2. The photodegradable filter rod according to claim 1, wherein The filter rod is selected from one or more of a diacetate fiber tow or a propylene fiber tow filter rod.

3. The photodegradable filter rod according to claim 1, wherein The plasticizer is selected from one or more of triacetin or tributyrin.

4. The photo-degradable filter rod according to claim 1, characterized in that, The photocatalytic degradation catalyst is titanium dioxide.

5. The photodegradable filter rod according to claim 1, wherein The photosensitizer is selected from one or more of sodium copper chlorophyllin, methylene blue, rose bengal or porphyrin.

6. The photo-degradable filter rod according to claim 1, characterized in that, It includes at least one of the following technical features: A1) The mass ratio of the filter rod to the photocatalytic degradation catalyst is 7:100000 to 15:100000; A2) The mass ratio of the photosensitizer to the photocatalytic degradation catalyst is 1.00 to 100.00; A3) The mass ratio of the photocatalyst to the plasticizer is (1:1000) to (1:100); A4) The mass ratio of the plasticizer to the filter rod is (7:100) to (15:100).

7. The photo-degradable filter rod according to claim 3, characterized in that, The titanium dioxide is selected from one or more of anatase titanium dioxide and titanium dioxide P25.

8. The preparation method of the photo-degradable filter rod according to any one of claims 1-7, characterized in that, It includes spraying the photocatalyst and the plasticizer on the filter rod after mixing, and then immersing the filter rod in the photosensitizer solution and drying it to obtain the photocatalytic degradation filter rod.

9. The preparation method of the photo-degradable filter rod according to claim 8, characterized in that, It includes at least one of the following technical features: B1) During the mixing, use a blender for the first stirring until it becomes a suspension state; B2) Before the spraying, loosen the filter rod; B3) The solvent of the photosensitizer solution is selected from one or more of water, ethanol or acetone; B4) When preparing the photosensitizer solution, use a blender for the second stirring; B5) The immersion time is 24 to 36 h; B6) During the immersion, the number of filter rods immersed in every 1000 mL of the photosensitizer solution is 200 to 400; B7) The drying temperature is 40 to 50 °C; B8) The drying time is 24 to 36 h.

10. The preparation method of the photo-degradable filter rod according to claim 9, characterized in that, It includes at least one of the following technical features: B11) In feature B1), the rotation speed of the first stirring is 500 to 1000 r / min; B12) In feature B1), the time of the first stirring is 20 to 45 min; B31) In feature B3), the mass ratio of the photosensitizer to the solvent is (0.1:100) to (1:100); B41) In feature B4), the rotation speed of the second stirring is 200 to 550 r / min; B42) In feature B4), the time of the second stirring is 15 to 30 min.

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