A loaded ethylene ripening agent and its preparation method and application

Abstract

The invention provides a loaded ethylene ripening agent, a preparation method thereof, and an application thereof, belonging to the technical field of fruit and vegetable ripening. The invention mainly provides a loaded ethylene ripening agent, comprising activated carbon adsorbed with ethylene and a packaging material. The preparation method of the loaded ethylene ripening agent comprises the following steps: quantitatively packaging the activated carbon with an inner packaging material, sealing the activated carbon to obtain an activated carbon bag, placing the activated carbon bag in a sealed container, filling the container with ethylene gas, and embedding the bag for 0.5 to 24 hours, wherein the embedding method is normal pressure embedding or high pressure embedding; the pressure of the high pressure embedding is 0.5 to 3 MPa, and the activated carbon bag adsorbed with ethylene is obtained. The loaded ethylene ripening agent is applied in the ripening field. The ripening agent prepared by the invention has good ripening effect, can directly contact fruits and vegetables, does not accumulate, has no odor, and does not leave residue, is environmentally friendly, has a simple preparation method, and is low in cost.

Description

Technical Field

[0001] The invention belongs to the technical field of fruit and vegetable ripening, and particularly relates to a loaded ethylene ripening agent and a preparation method and application thereof. Background Art

[0002] At present, there are various forms of products for preserving and ripening, such as packaging boxes, packaging bags, ripening bags, ripening liquids, etc. that can preserve or ripen fruits and vegetables; different ways of using the products are also diverse; for example, fruits and vegetables that need to be preserved or ripened can be directly placed in packaging boxes or packaging bags with such functions; or ripening bags can be placed directly into fruits and vegetables to be ripened, or ripening liquid can be directly sprayed onto fruits and vegetables to be ripened.

[0003] Ripening-promoting packaging boxes and bags are complex and expensive to use for fruit and vegetable growth. Spraying ripening liquid directly onto fruits and vegetables can easily cause them to overripen or burn. Ripening bags are less expensive and more convenient to use than ripening devices. They also have a milder ripening effect and are more food-safe.

[0004] In the prior art, the main ripening ingredient in ripening bags is ethephon. Ethephon is stable in aqueous solution at a pH less than 3.5 and releases ethylene through hydrolysis as the pH increases. Therefore, existing commercially available ripening bags must be soaked in water before being placed in fruits and vegetables to promote ripening. The conversion rate of the ethephon slow-release agent is low (50-80%), and there is a risk of damage. Leaked raw materials may cause environmental pollution, and residues on fruits and vegetables may be harmful to the human body, posing safety risks. Another problem is that the residue after the ethylene is released is an inorganic and organic mixture, which pollutes the environment.

[0005] There are also reports on the direct use of ethylene gas for ripening. Commonly used gas adsorption carriers include porous carriers such as activated carbon, carbon nanotubes, and zeolites. Currently, these carriers are mainly used to separate and adsorb ethylene gas mixtures or remove ethylene gas from stored fruits and vegetables. Ethylene-loaded carriers such as activated carbon, carbon nanotubes, and zeolites are relatively expensive and have unstable ethylene-entrapment capabilities. They are currently primarily used for ethylene adsorption and removal, and there are few reports on ripening agents that directly load ethylene.

[0006] Chinese patent document CN108371180A (application number: 201810223219.6) discloses an ethylene gas embedding material with sustained-release properties and an embedding method. The embedding method comprises placing cucurbituril in a high-pressure reactor, adding 10-40% of the reactor volume, evacuating the reactor, introducing ethylene gas, controlling the pressure at 0.1-2.0 MPa, and reacting at 15-35°C for 8-48 hours. After the reaction is completed, the outlet valve of the reactor is opened to absorb the unabsorbed ethylene to obtain an ethylene-embedded product with sustained-release properties. The cucurbituril raw material is expensive, which is not conducive to its promotion and application.

[0007] Chinese patent document CN215555500U (application number: 202121825981.5) discloses a fruit ripening packaging bag. The packaging bag disclosed in this utility model patent includes a bag body, a lid and a rope. The outer surface of the bag body is provided with a waterproof coating, and the inner side of the bag body is provided with a slow-release structure. The slow-release structure includes activated carbon particles, a non-woven fiber layer, air holes and grooves. The non-woven fiber layer is installed on the inner side of the bag body, and a groove is provided between the non-woven fiber layer and the bag body. The inside of the groove is filled with activated carbon particles. The non-woven fiber layer is evenly provided with air holes. A lid is installed on the top of the bag body, and a rectangular raised inner cover is provided on the inner surface of the lid. The ripening packaging bag provided by this utility model has a complex structure and a high production cost. In addition, when using it, it is necessary to add fruit into the ripening packaging bag. When ripening a large amount of fruit, the use cost is high. It does not record how the activated carbon particles can achieve the slow release of ethylene to the fruit in the bag, and the role of modified activated carbon. Summary of the Invention

[0008] In view of the deficiencies in the prior art, the present invention provides a loaded ethylene ripening agent and a preparation method and application thereof.

[0009] Terminology

[0010] Inner packaging material: refers to the packaging material that is in direct contact with activated carbon.

[0011] Outer packaging material: refers to the packaging material that does not directly contact the activated carbon. The outer packaging material is packaged outside the inner packaging material.

[0012] The technical solutions of the present invention are as follows:

[0013] A loaded ethylene ripening agent comprises activated carbon adsorbed with ethylene and a packaging material.

[0014] Preferably, according to the present invention, the mass percentage of ethylene adsorbed by the activated carbon is 0.4-15%.

[0015] Further preferably, the mass percentage of ethylene adsorbed by the activated carbon is 1 to 15%.

[0016] According to the preferred embodiment of the present invention, the packaging material includes an inner packaging material, and the moisture permeability of the inner packaging material is in the range of 5 to 3000 g / m 2 .24h.

[0017] More preferably, the moisture permeability of the inner packaging material is in the range of 10 to 100 g / m 2 .24h.

[0018] Further preferably, the inner packaging material includes water-soluble film, coated paper, composite non-woven fabric, non-woven fabric, plastic film, aluminum foil, and filter paper.

[0019] Preferably according to the present invention, the packaging material further comprises an outer packaging material, and the outer packaging material is impermeable to ethylene.

[0020] More preferably, the outer packaging material includes aluminum foil, aluminum foil composite film, or PET / PE composite film.

[0021] Preferably according to the present invention, the activated carbon packaging amount of the ripening agent in the inner packaging material is more than 0.1g per package.

[0022] More preferably, the activated carbon packaging amount of the inner packaging material is 0.1 to 1000 g per package.

[0023] More preferably, the activated carbon packaging amount of the inner packaging material is 0.5 to 10 g per package.

[0024] Preferably according to the present invention, the internal pore diameter of the activated carbon is 16 to 40 microns.

[0025] More preferably, the internal pore diameter of the activated carbon is 25 to 40 microns.

[0026] Preferably according to the present invention, the activated carbon is in powder or granular form.

[0027] More preferably, the activated carbon is in granular form.

[0028] More preferably, the diameter of the activated carbon particles is 4 to 50 meshes.

[0029] More preferably, the diameter of the activated carbon particles is 5 to 25 meshes.

[0030] According to the present invention, the activated carbon preferably includes one or more of coal-based activated carbon, coconut shell activated carbon, fruit shell activated carbon, and wood activated carbon.

[0031] Further preferably, the activated carbon is coal-based activated carbon or coconut shell activated carbon.

[0032] Preferably according to the present invention, the activated carbon is modified activated carbon.

[0033] Further preferably, the preparation method I of modified activated carbon comprises the following steps:

[0034] The activated carbon is washed and dried to obtain modified activated carbon.

[0035] Further preferably, the washing method includes one or more of ultrasonic cleaning, immersion, and rinsing;

[0036] The washing liquid includes water and / or an aqueous solution.

[0037] More preferably, the solute of the aqueous solution is a surfactant and / or a water-absorbing component;

[0038] The surfactant includes one or more of dodecyltrimethylammonium chloride, sodium lignin sulfonate, calcium lignin sulfonate, sodium dibutylnaphthalene sulfonate formaldehyde condensate, sodium naphthalene sulfonate formaldehyde condensate, sodium hexametaphosphate, sodium tripolyphosphate, alkyl sulfate, dodecylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl succinic acid sulfonate, and soapberry powder;

[0039] The water-absorbing component includes one or more of magnesium sulfate, calcium chloride, glucose, sodium sulfate, and ammonium chloride.

[0040] More preferably, the drying method includes vacuum drying, forced air drying, and fluidized bed drying.

[0041] Further preferably, the preparation method II of modified activated carbon comprises the following steps:

[0042] The activated carbon is calcined at a temperature of 200 to 800° C. and a calcination time of 2 to 24 hours to obtain modified activated carbon.

[0043] The preparation method of the above-mentioned supported ethylene ripening agent comprises the following steps:

[0044] (1) quantitatively packaging the activated carbon with an inner packaging material and sealing the package to obtain an activated carbon package;

[0045] (2) The activated carbon bag obtained in step (1) is placed in a sealed container, filled with ethylene gas and embedded for 0.5 to 24 hours. The embedding method is normal pressure embedding or high pressure embedding. The pressure of high pressure embedding is 0.5 to 3 MPa, and an activated carbon bag adsorbed with ethylene is obtained, which is a loaded ethylene ripening agent.

[0046] According to a preferred embodiment of the present invention, in step (2), the activated carbon bag that has adsorbed ethylene is packaged with an outer packaging material that is impermeable to ethylene and sealed.

[0047] The application of the above-mentioned loaded ethylene ripening agent in the field of ripening.

[0048] Preferably, according to the present invention, the supported ethylene ripening agent is used in ripening fruits and vegetables.

[0049] More preferably, the fruits and vegetables include mangoes and bananas.

[0050] More preferably, the amount of the supported ethylene ripening agent used per kilogram of mango is 0.01 to 5 g, calculated by weight of the activated carbon; and the amount of the supported ethylene ripening agent used per kilogram of banana is 0.001 to 2 g, calculated by weight of the activated carbon.

[0051] The method for using the above-mentioned supported ethylene ripening agent comprises the following steps:

[0052] Place the loaded ethylene ripening agent directly into the fruit and vegetable packaging and manage it according to conventional ripening temperature and humidity conditions;

[0053] Alternatively, the loaded ethylene ripening agent can be soaked in water, taken out, and then placed directly in the fruit and vegetable packaging, and managed according to conventional ripening temperature and humidity conditions.

[0054] Beneficial effects

[0055] 1. The ripening agent provided by the present invention uses raw materials from a wide range of sources, is cheap and easily available, is easy to use, does not contain ethephon, has no chemical reaction when used, can directly contact fruits and vegetables, does not accumulate, has no odor, and does not leave residue, is environmentally friendly, has a simple structure, and has a low production cost.

[0056] 2. The ripening agent provided by the present invention is easy to use, and the product release rate is not affected by the ambient humidity and has a fast release speed.

[0057] 3. The ripening agent provided by the present invention can achieve appropriate embedding and releasing effects by adjusting the moisture permeability of the inner packaging material according to the needs of use. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] Figure 1 This is the SEM test result of unmodified activated carbon.

[0059] Figure 2 This is the SEM test result of modified activated carbon. DETAILED DESCRIPTION

[0060] The present invention will be further described below with reference to the following examples, but the protection scope of the present invention is not limited thereto.

[0061] The contents not described in detail in the examples are based on the prior art in this field.

[0062] Sources of main materials

[0063] The activated carbon used in the following examples was mainly sourced from the following manufacturers, see Table 1:

[0064] Table 1

[0065] factory Activated carbon material Number of meshes (mesh) Jiangsu-Mulinsen coconut shell 40-80 Jiangsu-Zhuxi Nutshell 200 Shanghai-Ning Ran coconut shell 16～30 Jiangsu-Sensen coal quality 8～20 Jiangsu-Chengsen coal quality 8～16 Suzhou-Jushengyuan coal quality 8～16 Shandong-South China Science Park coal quality 8～16 Jiangsu-Bits coconut shell 8～16 Durban, Hunan coal quality 4～8 Anguo Chengze coconut shell 10～20 Tianjin-Tianyuan coal quality 8～16

[0066] The following average values ​​of the internal pore diameter of activated carbon are the average values ​​of 10 pore diameters randomly measured by SEM on the internal cavity of activated carbon.

[0067] In the following embodiments, the outer packaging refers to the outer packaging material, and the inner packaging refers to the inner packaging material.

[0068] Experimental Example 1

[0069] The preparation method of modified activated carbon comprises the following steps:

[0070] 8-16 mesh coconut shell granular activated carbon was impregnated with 10% by mass glucose solution, filtered, and then dried under reduced pressure at 60° C. until the moisture content was less than 2% to prepare modified activated carbon.

[0071] Activated carbon characterization test: SEM was used to test the surface morphology of unmodified activated carbon and modified activated carbon. The test results are shown in Figure 1 、 Figure 2 .

[0072] Figure 1 This is the SEM test result of unmodified activated carbon. The pore size of the activated carbon is about 20 microns.

[0073] Figure 2 This is the SEM test result of modified activated carbon. The pore size of activated carbon is about 30 microns. The pore size of activated carbon has changed after modification.

[0074] Experimental Example 2

[0075] Effects of different activated carbon modification methods on ethylene adsorption

[0076] Calcination: Place the activated carbon in a crucible, put it into a muffle furnace, set the required temperature, and calcine for 2 to 24 hours.

[0077] Impregnation solution treatment: The activated carbon is completely soaked with different solutions, filtered, and dried under reduced pressure.

[0078] Ethylene entrapment capacity test: 6×6 cm packets, made with heat-sealable filter paper inner packaging, were filled with 2.5 g of activated carbon with different modifications. Each packet was placed in a 450×550 cm 10-filament aluminum foil bag, filled with 99.99% ethylene gas, sealed, and entrapped at room temperature and pressure for 24 hours. After removal, each packet was placed in a 1 L headspace bottle and tested for maximum ethylene release, which was used as the ethylene adsorption capacity (see Table 2).

[0079] Table 2 Effect of different activated carbon modification methods on ethylene adsorption

[0080]

[0081] Experimental Example 3

[0082] Effects of different moisture permeability packaging materials on ethylene encapsulation performance

[0083] (1) Ethylene embedding capacity test: Coal-based activated carbon was impregnated with a 5% sodium dodecylbenzenesulfonate aqueous solution, filtered, and placed in a vacuum drying oven. Drying was carried out at 80°C under reduced pressure until the moisture content was less than 1%. 6×10 cm small packages were prepared using different inner packaging materials. 3 g of activated carbon was weighed into each package and heat-sealed. The small packages were placed in a 250 mL high-pressure reactor and 99.99% ethylene gas was introduced to a pressure of 1.5 MPa. The reaction was carried out at 25°C for 24 hours. After the reaction was completed, the inlet valve was closed and the outlet valve was opened. Unabsorbed ethylene was absorbed with potassium permanganate. After removal, each small package was placed in a 1 L headspace bottle to test the maximum ethylene release, thereby calculating the ethylene adsorption capacity.

[0084] (2) Moisture permeability test method:

[0085] Test method: GB / T 1037-1988 cup method. Test results are shown in Table 3.

[0086] Water vapor transmission rate unit: g / m 2 .24h;

[0087] Test temperature: 38℃±0.5℃;

[0088] Relative humidity: 90%±2%.

[0089] Table 3

[0090]

[0091] Example 1

[0092] A loaded ethylene ripening agent, the outer packaging is a 10-filament aluminum foil bag 180×250mm, the inner packaging is a 30×30mm heat-sealed small package of coated paper sample, each small package contains 0.1g of 4-8 mesh granular coal-based activated carbon, with an average internal pore size of 21 microns.

[0093] Preparation method: Place the small packages wrapped in inner packaging in a sealed container, evacuate to -0.1 MPa, then fill with 99.99% ethylene gas, and continuously replenish ethylene gas to maintain normal pressure for 16 hours. Take out the small packages, 200 small packages / package, and pack them with outer packaging.

[0094] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 1.5%.

[0095] Example 2

[0096] A loaded ethylene ripening agent, the outer packaging is a 10-filament aluminum foil bag 180×250mm, the inner packaging is a laminated paper sample 1 heat-sealed small package 30×35mm, each small package contains 1.0g of 40-80 mesh granular coconut shell activated carbon, with an average internal pore size of 25 microns.

[0097] Preparation method: Place the small packages wrapped in inner packaging in a sealed container, evacuate to -0.2 MPa, then fill with 99.99% ethylene gas to a pressure of 0.5 MPa, maintain the pressure for 20 hours, take out the small packages, 100 small packages / package, and pack them with outer packaging.

[0098] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 8.3%.

[0099] Example 3

[0100] A loaded ethylene ripening agent, the outer packaging is a 10-wire aluminum foil bag 180×250mm, the inner packaging is a laminated paper sample 2 heat-sealed small package 50×45mm, each small package contains 2.5g 8-16 mesh granular coal-based activated carbon, with an average internal pore size of 23 microns.

[0101] Preparation method: Place the small packages wrapped in inner packaging in a sealed container, evacuate to -0.1 MPa, fill with 99.99% ethylene gas to a pressure of 3.0 MPa, maintain the pressure for 24 hours, take out the small packages, 50 small packages / package, and pack them with outer packaging.

[0102] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 2.5%.

[0103] Example 4

[0104] A loaded ethylene ripening agent, the outer packaging is a 10-wire aluminum foil bag 130×180mm, the inner packaging is a laminated paper sample 2 heat-sealed small package 50×45mm, each small package contains 2.5g 200-mesh granular fruit shell activated carbon, with an average internal pore size of 28 microns.

[0105] Preparation method: Place the small packages wrapped in inner packaging in a sealed container, evacuate to -0.1 MPa, then fill with 99.99% ethylene gas, and continue to replenish ethylene gas to maintain normal pressure for 16 hours. Take out the small packages, 20 small packages / package, and pack them with outer packaging.

[0106] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 2.0%.

[0107] Example 5

[0108] A loaded ethylene ripening agent, the outer packaging is a 10-filament aluminum foil bag 180×250mm, the inner packaging is a laminated paper sample 3 heat-sealed small package 60×55mm, each small package contains 10.0g 8-16 mesh granular coal-based activated carbon, with an average internal pore size of 20 microns.

[0109] Preparation method: Place the small packets wrapped in inner packaging in a sealed container, evacuate to -0.1 MPa, then fill with 99.99% ethylene gas, and continue to replenish ethylene gas to maintain normal pressure for 16 hours. Take out the small packets, 20 small packets / pack, and pack them with outer packaging.

[0110] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 0.4%.

[0111] Example 6

[0112] A loaded ethylene ripening agent, the outer packaging is a 10-filament aluminum foil bag 180×250mm, the inner packaging is a water-soluble film-like heat-sealed small package 30×40mm, each small package contains 1.0g of 10-20 mesh granular coconut shell activated carbon, with an average internal pore size of 26 microns.

[0113] Preparation method: Place the small packages wrapped in inner packaging in a sealed container, evacuate to -0.1 MPa, then fill with 99.99% ethylene gas to a pressure of 2.0 MPa, maintain the pressure for 16 hours, take out the small packages, 100 small packages / package, and pack them with outer packaging.

[0114] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 4.0%.

[0115] Example 7

[0116] A loaded ethylene ripening agent, with an outer packaging of a 10-filament aluminum foil bag (200×300mm) and an inner packaging of two heat-sealed composite non-woven fabric bags (30×50mm). Each bag contains 1.5g of 16-30 mesh granular coconut shell activated carbon with an average internal pore size of 26 microns.

[0117] Preparation method: Place the small packages wrapped in inner packaging in a sealed container, evacuate to -0.1 MPa, then fill with 99.99% ethylene gas to a pressure of 1.8 MPa, maintain the pressure for 20 hours, take out the small packages, 100 small packages / package, and pack them with outer packaging.

[0118] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 2.50%.

[0119] Example 8

[0120] A loaded ethylene ripening agent, the outer packaging is a 12-filament PET / PE bag 200×300mm, the inner packaging is a PE sample 1 heat-sealed small package 60×50mm, each small package contains 4.0g 8-16 mesh granular coconut shell activated carbon, with an average internal pore size of 23 microns.

[0121] Preparation method: Place the small packages wrapped in inner packaging in a sealed container, evacuate to -0.1 MPa, fill with 99.99% ethylene gas to a pressure of 3.0 MPa, maintain the pressure for 24 hours, take out the small packages, 50 small packages / package, and pack them in outer packaging.

[0122] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 4.2%.

[0123] Example 9

[0124] A loaded ethylene ripening agent, with an outer packaging of a 12-filament aluminum foil composite bag, 200×300mm, and an inner packaging of a perforated aluminum foil sample bag, 60×45mm. Each small package contains 3.50g of 10-20 mesh granular coconut shell activated carbon, with an average internal pore size of 26 microns.

[0125] Preparation method: Place the small packages wrapped in inner packaging in a sealed container, evacuate to -0.1 MPa, fill with 99.99% ethylene gas to a pressure of 3.0 MPa, maintain the pressure for 24 hours, take out the small packages, 50 small packages / package, and pack them with outer packaging.

[0126] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 1.0%.

[0127] Example 10

[0128] A loaded ethylene ripening agent, with an outer packaging of a 14-filament aluminum foil bag 250×300mm and an inner packaging of a composite non-woven fabric-like heat-sealed package 220×250mm. Each small package contains 1000g of 8-20 mesh granular coal-based activated carbon with an average internal pore size of 16 microns.

[0129] Preparation method: Place the small package wrapped in inner packaging in a reaction device, fill it with 99.99% ethylene gas, and continuously replenish ethylene gas to maintain normal pressure for 24 hours. Take out the small package, 1 small package / package, and pack it with outer packaging.

[0130] A small bag was placed in a 1 cubic meter tent and the maximum ethylene release was 2.7%.

[0131] Example 11

[0132] A loaded ethylene ripening agent, the outer packaging is a 10-wire aluminum foil bag 180×250mm, the inner packaging is a laminated paper sample 1 heat-sealed small package 30×30mm, each small package contains 0.1g of modified activated carbon, and the average internal pore size is 22 microns.

[0133] The 4-8 mesh granular coal-based activated carbon in Example 1 was modified to prepare modified activated carbon.

[0134] Preparation method: Rinse 4-8 mesh granular coal-based activated carbon with flowing pure water, filter, and then air-dry at 90°C until the moisture content is less than 2% to produce modified activated carbon. Use inner packaging to pack into small packets, place the small packets in a sealed container, evacuate to -0.1 MPa, and then fill with 99.99% ethylene gas. Continue to add ethylene gas to maintain normal pressure for 16 hours, remove the small packets, 200 packets / pack, and pack with outer packaging.

[0135] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 1.9%.

[0136] Example 12

[0137] A loaded ethylene ripening agent, the outer packaging is a 10-wire aluminum foil bag 180×250mm, the inner packaging is a laminated paper sample 1 heat-sealed small package 30×35mm, each small package contains 1.0g of modified activated carbon, and the average internal pore size is 32 microns.

[0138] The 40-80 mesh granular coconut shell activated carbon in Example 2 was modified to prepare modified activated carbon.

[0139] Preparation method: 40-80 mesh granular coconut shell activated carbon is impregnated with 1.5 times the volume of a 15% sodium dodecylbenzenesulfonate aqueous solution, filtered using a suction filtration device, and then dried in a fluidized bed at 70°C until the moisture content is less than 2% to produce modified activated carbon. The modified activated carbon is then packaged into small packets using inner packaging. The small packets are placed in a reaction apparatus, evacuated to -0.2 MPa, and then filled with 99.99% ethylene gas to a pressure of 0.5 MPa. The pressure is maintained for 20 hours, and the small packets are removed, with 100 packets per packet, and then packaged in outer packaging.

[0140] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 14.5%.

[0141] Example 13

[0142] A loaded ethylene ripening agent, the outer packaging is a 10-wire aluminum foil bag 180×250mm, the inner packaging is a laminated paper sample 2 heat-sealed small package 50×45mm, each small package contains 2.5g of modified activated carbon, and the average internal pore size is 27 microns.

[0143] The 8-16 mesh granular coal-based activated carbon in Example 3 was modified to prepare modified activated carbon.

[0144] Preparation method: Add 8-16 mesh granular coal-based activated carbon to 2.0 times the volume of a 10% calcium lignin sulfonate aqueous solution, ultrasonically clean for 60 minutes, filter using a suction filtration device, and then vacuum dry the activated carbon at 60°C until the moisture content is less than 2% to produce modified activated carbon. Use inner packaging to pack into small packages, place the small packages in a reaction device, evacuate to -0.1 MPa, and fill with 99.99% ethylene gas to a pressure of 3.0 MPa. Maintain the pressure for 24 hours, remove the small packages, 50 small packages per package, and pack them with outer packaging.

[0145] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 5.1%.

[0146] Example 14

[0147] A loaded ethylene ripening agent, the outer packaging is a 10-wire aluminum foil bag 130×180mm, the inner packaging is a laminated paper sample 2 heat-sealed small package 50×45mm, each small package contains 2.5g of modified activated carbon, and the average internal pore size is 34 microns.

[0148] The 200-mesh granular fruit shell activated carbon in Example 4 was modified to prepare modified activated carbon.

[0149] Preparation method: Calcine 200-mesh granular activated carbon from fruit shells at 200°C for 24 hours to produce modified activated carbon. Use inner packaging to pack the activated carbon into small packets. Place the packets in a reaction vessel, evacuate to -0.1 MPa, and then fill with 99.99% ethylene gas. Continue replenishing ethylene gas to maintain atmospheric pressure for 16 hours. Remove the packets (20 packets / pack) and pack them in outer packaging.

[0150] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 6.0%.

[0151] Example 15

[0152] A loaded ethylene ripening agent, the outer packaging is a 10-wire aluminum foil bag 180×250mm, the inner packaging is a laminated paper sample 3 heat-sealed small package 60×55mm, each small package contains 10.0g of modified activated carbon, and the average internal pore size is 27 microns.

[0153] The 8-16 mesh granular coal-based activated carbon in Example 5 was modified to obtain modified activated carbon.

[0154] Preparation method: Calcine 8-16 mesh granular coal-based activated carbon at 400°C for 10 hours to produce modified activated carbon. Use inner packaging to pack into small packages, place the small packages in the reaction device, evacuate to -0.1 MPa, and then fill with 99.99% ethylene gas. Continue to replenish ethylene gas to maintain normal pressure for 16 hours. Remove the small packages, 20 small packages per package, and pack them in outer packaging.

[0155] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 3.9%.

[0156] Example 16

[0157] A loaded ethylene ripening agent, the outer packaging is a 10-wire aluminum foil bag 180×250mm, the inner packaging is a water-soluble film sample 1 heat-sealed small package 30×40mm, each small package contains 1.0g of modified activated carbon, and the average internal pore size is 34 microns.

[0158] The 10-20 mesh granular coconut shell activated carbon in Example 6 was modified to prepare modified activated carbon.

[0159] Preparation method: Calcine 10-20 mesh granular coconut shell activated carbon at 800°C for 2 hours to produce modified activated carbon. Use inner packaging to pack into small packages, place the small packages in the reaction device, evacuate to -0.1 MPa, then fill with 99.99% ethylene gas to a pressure of 2.0 MPa. Maintain the pressure for 16 hours, remove the small packages, 100 small packages / package, and pack them in outer packaging.

[0160] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 5.3%.

[0161] Example 17

[0162] A loaded ethylene ripening agent, the outer packaging is a 10-filament aluminum foil bag 200×300mm, the inner packaging is a composite non-woven fabric sample 2 heat-sealed small packages 30×50mm, each small package contains 1.5g of modified activated carbon, and the average internal pore size is 27 microns.

[0163] The 16-30 mesh granular coconut shell activated carbon in Example 7 was modified to prepare modified activated carbon.

[0164] Preparation method: Add 16-30 mesh granular coconut shell activated carbon to purified water and soak at room temperature for 30 minutes. Filter the mixture using a suction filtration device. Then, place the activated carbon in a forced air drying oven set at 90°C and dry until the moisture content is less than 2% to obtain modified activated carbon. Use inner packaging to package the activated carbon into small packets. Place the small packets in a reaction device, evacuate to -0.1 MPa, then fill with 99.99% ethylene gas to a pressure of 1.8 MPa. Maintain the pressure for 20 hours. Remove the small packets, 100 packets per packet, and package them in outer packaging.

[0165] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 4.6%.

[0166] Example 18

[0167] A loaded ethylene ripening agent, the outer packaging is a 12-filament PET / PE bag 200×300mm, the inner packaging is a PE sample 1 heat-sealed small package 60×50mm, each small package contains 4.0g of modified activated carbon, and the average internal pore size is 30 microns.

[0168] The 8-16 mesh granular coconut shell activated carbon in Example 8 was modified to prepare modified activated carbon.

[0169] Preparation method: Add 8-16 mesh granular coconut shell activated carbon to 5 times the volume of 10% ammonium chloride aqueous solution, ultrasonically clean for 60 minutes, filter using a suction filtration device, and then vacuum dry the activated carbon at 60°C until the moisture content is less than 2% to produce modified activated carbon. Use inner packaging to pack into small packets, place the small packets in a reaction device, evacuate to -0.1 MPa, and fill with 99.99% ethylene gas to a pressure of 3.0 MPa. Maintain the pressure for 24 hours, remove the small packets, 50 packets per packet, and pack them in outer packaging.

[0170] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 6.1%.

[0171] Example 19

[0172] A loaded ethylene ripening agent, the outer packaging is a 12-filament aluminum foil composite bag 200×300mm, the inner packaging is a perforated aluminum foil sample small package 60×45mm, each small package contains 3.50g of modified activated carbon, and the average internal pore size is 34 microns.

[0173] The 10-20 mesh granular coconut shell activated carbon in Example 9 was modified to prepare modified activated carbon.

[0174] Preparation method: Add 10-20 mesh granular coconut shell activated carbon to 5 times the volume of 5% glucose aqueous solution, ultrasonically clean for 60 minutes, filter using a suction filtration device, and then boil and dry the activated carbon at 60°C until the moisture content is less than 1.5% to produce modified activated carbon. Use inner packaging to package it into small packets, place the small packets in a reaction device, evacuate to -0.1 MPa, and fill with 99.99% ethylene gas to a pressure of 3.0 MPa. Maintain the pressure for 24 hours, remove the small packets, 50 packets per packet, and package them in outer packaging.

[0175] A small packet was placed in a 1 L headspace bottle to test the maximum ethylene release, which was 3.2%.

[0176] Example 20

[0177] A loaded ethylene ripening agent, with an outer packaging of a 14-filament aluminum foil bag 250×300mm and an inner packaging of a composite non-woven fabric sample 1 heat-sealed package 220×250mm. Each small package contains 1000g of modified activated carbon, with an average internal pore size of 18 microns.

[0178] The 8-20 mesh granular coal-based activated carbon in Example 10 was modified to obtain modified activated carbon.

[0179] Preparation method: Add 8-20 mesh granular coal-based activated carbon to 5 times the volume of a 5% composite alkyl sulfate + 10% ammonium chloride aqueous solution, soak for 30 minutes, filter using a suction filtration device, and then air-dry the activated carbon at 90°C until the moisture content is less than 1.0% to produce modified activated carbon. Use inner packaging to package it into small packages, place the small packages in a reaction device, fill it with 99.99% ethylene gas, and continuously replenish ethylene gas to maintain normal pressure for 24 hours. Remove the small packages, one small package per package, and package them with outer packaging.

[0180] A small package was placed in a 1 cubic meter tent and the maximum ethylene release was 3.5%.

[0181] Effect Examples

[0182] Application of the above embodiment in preparing loaded ethylene ripening agent

[0183] (1) The ripening agents prepared in Examples 1 to 20 were used to ripen fruits. The test fruit varieties were green-ripe bananas (green-ripe means that the fruit has reached the ripening condition, but the skin is still green) and mangoes.

[0184] Test method:

[0185] Banana ripening: Evenly group bananas into groups of 3 parallel bananas. Pack bananas into commercially available PVC bags, tie the bags, and place them in cardboard boxes. Open the side of the bag and place a packet of ripening agent (not wet) into each parallel banana. Maintain an ambient temperature of approximately 20°C and a relative humidity of above 98%. Observe the bananas daily and record the average ripening period.

[0186] Mango ripening: Mangoes were evenly grouped into 3 parallel groups. They were packaged in commercially available mango cartons, with absorbent paper placed on the top, bottom, and between the mangoes. A packet of ripening agent (not wet) was placed in each parallel group. The ambient temperature was maintained at approximately 28°C and the relative humidity was maintained above 98%. The mangoes were observed daily and the average ripening period was recorded.

[0187] Table 4 Ripening period of different ripening agents

[0188]

[0189]

[0190] As shown in Table 4, the ripening agent of the present invention has a ripening period of 2 to 4 days for mangoes and bananas. The ripening effect of the ripening agent prepared with modified activated carbon is better than that of the ripening agent prepared with unmodified activated carbon under the same preparation conditions.

[0191] (2) Application of commercially available ripening agents and ripening agents prepared in Example 3

[0192] Test methods

[0193] Green ripe small mangoes without ripening treatment were purchased from Jinan Dikou Fruit Wholesale Market. Fresh mangoes without disease or mechanical damage were selected and randomly divided into 9 groups, with three replicates for each treatment.

[0194] Treatment 1: After opening the outer packaging of the ripening agent prepared in Example 3, quickly place it in clean water to soak for 15 seconds, take the medicine package and place it above the mango, quickly lay paper around it, and stack it;

[0195] Treatment 2: After opening the outer packaging of the ripening agent prepared in Example 3, take the medicine package and place it above the mangoes, quickly lay paper around it, and stack it;

[0196] Treatment 3: After opening the outer packaging of commercially available mango ripening agent (3.0 g per small package, 20% ethephon content), take the medicine package and place it above the mangoes, quickly lay paper around it, and stack it.

[0197] Maintain a temperature of 28°C and relative humidity >90%. Observe the appearance of the mangoes daily and determine the peel yellowing index based on the color change of the mangoes.

[0198] (2) Data statistical analysis

[0199] According to the survey results, Excel and PASS data processing software were used to calculate the experimental results, and the temperature and peel yellowing index of each treatment were calculated respectively.

[0200] Peel yellowing index:

[0201] The peel color is divided into 5 levels:

[0202] Level 0: all green;

[0203] Level 1: Slight yellowing at the fruit base (25%);

[0204] Level 2: The fruit base and other parts are partially yellowed (25% to 50%);

[0205] Level 3: About 50% to 75% of the peel surface turns yellow;

[0206] Level 4: Most of the peel (75%) turns yellow.

[0207]

[0208] (3) Experimental results and analysis

[0209] The mangoes treated with the commercially available mango ripening agent and the ripening agent prepared in Example 3 all turned yellow in 3-3.5 days, and the mangoes used directly all turned yellow and ripened in 2.5-3 days. The experimental results are shown in Table 5.

[0210] Table 5 Effects of different treatments on mango indicators

[0211]

[0212]

[0213] No phytotoxicity was observed in any treatment. The ripening agent prepared in Example 3 presented no risk of ethephon leakage compared to commercially available mango ripening agents. Mangoes treated with the commercially available mango ripening agent and the ripening agent prepared in Example 3, which was then used for soaking, essentially all turned yellow within 3-3.5 days. Mangoes treated directly with the ripening agent prepared in Example 3 all turned yellow and ripened within 2.5-3 days. Compared to commercially available mango ripening agents, the ripening period was shorter and there was no risk of ethephon leakage.

[0214] The ripening agent prepared by the present invention uses raw materials from a wide range of sources, is cheap and readily available, and is easy to use. The ripening agent is particularly effective compared to a ripening agent prepared after modified activated carbon. The ripening agent prepared by the present invention does not contain ethephon, eliminating the risk of ethephon leakage. The ripening agent does not react chemically during use, can directly contact fruits and vegetables, does not accumulate, does not have odor, and does not leave residue, is environmentally friendly, and has a simple preparation method and low cost.

Claims

1. A loaded ethylene ripening agent, characterized in that including activated carbon having adsorbed ethylene and packaging materials; The activated carbon is modified activated carbon; The preparation method of the modified activated carbon comprises the following steps: 40-80 mesh granular coconut shell activated carbon was added to a sodium dodecylbenzenesulfonate aqueous solution for washing, and then the activated carbon was dried to prepare modified activated carbon; The preparation method of the supported ethylene ripening agent comprises the following steps: (1) quantitatively packaging and sealing the modified activated carbon with an inner packaging material to obtain an activated carbon bag; (2) placing the activated carbon bag obtained in step (1) in a sealed container, filling it with ethylene gas and embedding it for 0.5 to 24 hours, wherein the embedding method is normal pressure embedding or high pressure embedding; the pressure of high pressure embedding is 0.5 to 3 MPa, and an activated carbon bag adsorbed with ethylene is obtained, which is a loaded ethylene ripening agent; In step (1), the inner packaging material includes a water-soluble film, coated paper, composite non-woven fabric, non-woven fabric or filter paper; The moisture permeability of the inner packaging material ranges from 32.09 to 3000 g / m 2 .24h; In step (2), the activated carbon bag that has adsorbed ethylene is packaged with an outer packaging material that is impermeable to ethylene and sealed.

2. The loaded ethylene ripening agent according to claim 1, wherein The modified activated carbon preparation method comprises the following steps: adding 40-80 mesh granular coconut shell activated carbon to a 15% sodium dodecylbenzene sulfonate aqueous solution for impregnation, filtering with a suction filtration device, and then drying the activated carbon in a fluidized bed at 70° C. until the moisture content is less than 2%, thereby obtaining the modified activated carbon.

3. The loaded ethylene ripening agent according to claim 1, wherein In step (2), the activated carbon bag obtained in step (1) is placed in a sealed container, and after vacuuming, 99.99% ethylene gas is filled into the container to a pressure of 0.5 MPa, and the pressure is maintained for 20 hours to obtain an activated carbon bag adsorbed with ethylene, which is a loaded ethylene ripening agent.

4. The loaded ethylene ripening agent according to claim 1, wherein In step (2), the outer packaging material includes aluminum foil, aluminum foil composite film or PET / PE composite film.

5. The loaded ethylene ripening agent according to claim 1, wherein The moisture permeability of the inner packaging material is in the range of 43.25~100g / m 2 .24h.

6. The loaded ethylene ripening agent according to claim 1, wherein The internal pore diameter of the activated carbon is 16 to 40 microns.

7. The loaded ethylene ripening agent according to claim 1, wherein The ripening agent has an activated carbon packaging amount of more than 0.1g per package.

8. The loaded ethylene ripening agent according to claim 7, wherein The activated carbon packaging quantity of the inner packaging material is 0.1~1000g per package.

9. The supported ethylene ripening agent according to claim 8, wherein The activated carbon packaging quantity of the inner packaging material is 0.5~10g per package.

10. The supported ethylene ripening agent according to claim 1, wherein The washing method includes one or more of ultrasonic cleaning, immersion, and flushing; The drying method includes vacuum drying, forced air drying or fluidized bed drying.

11. Use of the supported ethylene ripening agent according to any one of claims 1 to 10 in the field of ripening.

12. The use according to claim 11, characterized in that The application of the loaded ethylene ripening agent in ripening of fruits and vegetables.

13. The use according to claim 12, characterized in that The fruits and vegetables include mangoes or bananas.

14. The use according to claim 13, characterized in that The amount of the loaded ethylene ripening agent used per kilogram of mango is 0.01 to 5 g, calculated by weight of the activated carbon; and the amount of the loaded ethylene ripening agent used per kilogram of banana is 0.001 to 2 g, calculated by weight of the activated carbon.

15. A method for using the supported ethylene ripening agent according to any one of claims 1 to 10, comprising the following steps: Place the loaded ethylene ripening agent directly into the fruit and vegetable packaging and manage it according to conventional ripening temperature and humidity conditions; Alternatively, the loaded ethylene ripening agent can be soaked in water, taken out, and then placed directly in the fruit and vegetable packaging, and managed according to conventional ripening temperature and humidity conditions.

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