CN116058408A - Supported ethylene ripening agent and preparation method and application thereof - Google Patents

Abstract

The utility model provides a supported ethylene ripening agent and a preparation method and application thereof, which belong to the technical field of fruit and vegetable ripening, and mainly provide a supported ethylene ripening agent, comprising activated carbon adsorbed with ethylene and a packing material; the preparation method of the supported ethylene ripening agent comprises the steps of quantitatively packaging and sealing the activated carbon with an inner packaging material to obtain an activated carbon package, placing the activated carbon package in a closed container, and filling ethylene gas for embedding for 0.5-24 h, wherein the embedding mode is normal-pressure embedding or high-pressure embedding; the high-pressure embedding pressure is 0.5-3 mpa, and the activated carbon bag with ethylene adsorbed is prepared; the application of the supported ethylene ripening agent in the ripening field; the ripening agent prepared by the utility model has good ripening effect, can be directly contacted with fruits and vegetables, has no accumulation, no peculiar smell and no residue, is environment-friendly, and has simple preparation method and low cost.

Description

Supported ethylene ripening agent and preparation method and application thereof

Technical Field

The utility model belongs to the technical field of fruit and vegetable ripening, and particularly relates to a supported ethylene ripening agent, and a preparation method and application thereof.

Background

At present, various products are used for fresh-keeping and ripening, such as packaging boxes, packaging bags, ripening liquid and the like which can play a role in fresh-keeping or ripening; the products have various use modes; for example, fruits and vegetables which need to be kept fresh or ripened are directly put into a packaging box or a packaging bag with the functions; or directly placing the ripening bag into fruits and vegetables to be ripening, or directly spraying ripening liquid onto the fruits and vegetables to be ripening.

The packaging box and the packaging bag which can play a role in promoting ripening have complex structures and high use cost for promoting the growth of fruits and vegetables; the ripening liquid is directly sprayed on fruits and vegetables, so that the phenomena of over ripening, head burning and the like of the fruits are easily caused; the ripening bag has lower use cost and more convenient use compared with the ripening device. Compared with ripening liquid, the ripening bag has mild ripening effect and high food safety.

In the prior art, the ripening components in the ripening bag are mainly ethephon, and the ethephon is stable in aqueous solution when the pH value is less than 3.5 and is hydrolyzed along with the rise of the pH value to release ethylene, so that the ripening bag sold in the prior art is soaked in water and then put into fruits and vegetables to promote ripening when in use; the conversion rate of the ethephon sustained-release agent is not high (50-80%), the ethephon sustained-release agent is possibly damaged, the leaked raw materials possibly cause environmental pollution, and residues on fruits and vegetables have safety risks such as harm to human bodies; another problem is that the residue after ethylene release is an inorganic, organic mixture, polluting the environment.

The prior art also reports on ripening directly using ethylene gas. The common gas adsorption carriers are porous carriers such as active carbon, carbon nano tubes, zeolite and the like, and the carriers are mainly used for separating and adsorbing ethylene gas mixtures or removing ethylene gas in fruit and vegetable storage at present. The ethylene-supported carrier, such as active carbon, carbon nano tube, zeolite, and the like, has high cost, unstable ethylene embedding capacity, is basically used for absorbing and removing ethylene at present, and has few reports on ripening agent products directly supported with ethylene.

The Chinese patent document CN108371180A (application number: 201810223219.6) discloses an embedding substance of ethylene gas with slow release performance and an embedding method, wherein the embedding method is that cucurbituril is placed in a high-pressure reaction kettle, the addition amount is 10-40% of the volume of the reaction kettle, the reaction kettle is vacuumized, ethylene gas is introduced, the pressure is controlled to be 0.1-2.0 Mpa, the ethylene gas reacts for 8-48 h at 15-35 ℃, an air outlet valve of the reaction kettle is opened after the reaction is finished, and unadsorbed ethylene is absorbed, so that an ethylene embedded product with slow release performance is obtained; the cucurbituril raw material is expensive and is not beneficial to popularization and application.

The utility model discloses a fruit ripening packaging bag, which comprises a bag body, a cover and a rope, wherein a waterproof coating is arranged on the outer surface of the bag body, a slow release structure is arranged on the inner side of the bag body and comprises active carbon particles, a non-woven fabric fiber layer, air holes and grooves, the non-woven fabric fiber layer is arranged on the inner side of the bag body, the grooves are formed between the non-woven fabric fiber layer and the bag body, the active carbon particles are filled in the grooves, the air holes are uniformly formed in the non-woven fabric fiber layer, the cover is arranged at the top end of the bag body, and a rectangular raised inner cover is arranged on the inner surface of the cover. The ripening packaging bag provided by the utility model has a complex structure and high manufacturing cost, and fruits are required to be added into the ripening packaging bag when the ripening packaging bag is used, so that the use cost is high when a large amount of fruits are ripening, and the effect of slowly releasing ethylene and modified activated carbon to the fruits in the bag is not recorded.

Disclosure of Invention

Aiming at the defects of the prior art, the utility model provides a supported ethylene ripening agent, and a preparation method and application thereof.

Description of the terms

And (3) inner wrapping: refers to a packaging material that is in direct contact with activated carbon.

And (3) an outer wrapping material: refers to a packaging material which is not directly contacted with the activated carbon, and an outer packaging material is packaged outside the inner packaging material.

The technical scheme of the utility model is as follows:

a supported ethylene ripening agent comprises activated carbon adsorbed with ethylene and a packing material.

According to the utility model, the mass percentage of the activated carbon to adsorb ethylene is preferably 0.4-15%.

Further preferably, the mass percentage of the activated carbon to adsorb ethylene is 1-15%.

According to the utility model, the packaging material comprises an inner packaging material, and the moisture permeability of the inner packaging material is 5-3000 g/m ² .24h。

Further preferably, the moisture permeability of the inner wrapper is in the range of 10 to 100g/m ² .24h。

Further preferably, the inner wrapping material comprises a water-soluble film, a coated paper, a composite non-woven fabric, a plastic film, an aluminum foil and filter paper.

Preferably, according to the present utility model, the packaging material further comprises an outer packaging material, which is impermeable to ethylene.

Further preferably, the outer coating material comprises aluminum foil, aluminum foil composite film and PET/PE composite film.

According to the present utility model, the amount of the inner wrapper packed with activated carbon is preferably 0.1g or more per wrapper.

Further preferably, the packing amount of the activated carbon of the inner packing material is 0.1 to 1000g per pack.

More preferably, the packing amount of the activated carbon of the inner packing material is 0.5-10 g per pack.

According to the utility model, the activated carbon preferably has an internal pore size of 16 to 40 microns.

Further preferably, the activated carbon has an internal pore size of 25 to 40 μm.

According to a preferred embodiment of the present utility model, the activated carbon is in the form of powder or granules.

Further preferably, the activated carbon is in the form of granules.

Further preferably, the activated carbon particles have a diameter of 4 to 50 mesh.

More preferably, the activated carbon particles have a diameter of 5 to 25 mesh.

According to the utility model, the activated carbon preferably comprises one or more than two of coal activated carbon, coconut shell activated carbon, fruit shell activated carbon and wood activated carbon.

Further preferably, the activated carbon is coal activated carbon or coconut activated carbon.

According to a preferred embodiment of the present utility model, the activated carbon is a modified activated carbon.

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

and washing the activated carbon, and drying to obtain the modified activated carbon.

Further preferably, the washing mode comprises one or more than two of ultrasonic cleaning, dipping and flushing;

the washing liquid comprises water and/or an aqueous solution.

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

the surfactant comprises one or more than two of dodecyl trimethyl ammonium chloride, sodium lignin sulfonate, calcium lignin sulfonate, dibutyl sodium naphthalene sulfonate formaldehyde condensate, sodium hexametaphosphate, sodium tripolyphosphate, alkyl sulfate, dodecyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl succinic acid sulfonate and Chinese honeylocust fruit powder;

the water absorption component comprises one or more of magnesium sulfate, calcium chloride, glucose, sodium sulfate and ammonium chloride.

Further preferably, the drying mode comprises vacuum drying, forced air drying and ebullated bed drying.

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

calcining the activated carbon at the temperature of 200-800 ℃ for 2-24 hours to obtain the modified activated carbon.

The preparation method of the supported ethylene ripening agent comprises the following steps:

(1) Quantitatively packaging the activated carbon with an inner packaging material, and sealing to obtain an activated carbon package;

(2) Placing the activated carbon obtained in the step (1) in a closed container, and filling ethylene gas for embedding for 0.5-24 h, wherein the embedding mode is normal-pressure embedding or high-pressure embedding; the high-pressure embedding pressure is 0.5-3 mpa, and the activated carbon package adsorbed with ethylene is prepared, namely the supported ethylene ripening agent.

According to the present utility model, in the step (2), the activated carbon bag having absorbed ethylene is packed with an outer material impermeable to ethylene, and sealed.

The application of the supported ethylene ripening agent in the ripening field.

According to the utility model, the supported ethylene ripening agent is preferably applied to ripening of fruits and vegetables.

Further preferably, the fruits and vegetables comprise mangoes and bananas.

Further preferably, the amount of the supported ethylene ripening agent is 0.01-5 g per kg of mango according to the weight of the activated carbon; the dosage of the supported ethylene ripening agent is 0.001-2 g per kilogram of banana based on the weight of active carbon.

The application method of the supported ethylene ripening agent comprises the following steps:

directly placing the load type ethylene ripening agent into a fruit and vegetable package, and managing according to conventional ripening temperature and humidity conditions;

or, the load type ethylene ripening agent is soaked in water, taken out and then directly put in the fruit and vegetable package, and is managed according to the conventional ripening temperature and humidity conditions.

Advantageous effects

1. The ripening agent provided by the utility model has the advantages of wide sources of raw materials, low cost, easiness in obtaining, convenience in use, no ethephon, no chemical reaction during use, capability of directly contacting fruits and vegetables, no accumulation, no peculiar smell, no residue, environmental friendliness, simple structure of the ripening agent and low manufacturing cost.

2. The ripening agent provided by the utility model is convenient to use, the release rate of the ripening agent is not affected by environmental humidity, and the release rate is high.

3. The ripening agent provided by the utility model can play a proper embedding and releasing role by adjusting the moisture permeability of the inner packaging material according to the use requirement.

Drawings

FIG. 1 is a graph showing SEM test results of unmodified activated carbon.

Fig. 2 is a graph of SEM test results of the modified activated carbon.

Detailed Description

The present utility model is further illustrated by the following examples, but the scope of the present utility model is not limited thereto.

What is not described in detail in the examples is known in the art.

Sources of the principal materials

The activated carbon used in the examples below was derived mainly from the following manufacturers, see table 1:

TABLE 1

Manufacturer' s	Activated carbon material	Mesh number (mesh)
			Jiangsu-wood Lin Sen	Coconut shell	40-80
Jiangsu-Zhixi	Shell of fruit	200
			Shanghai-Nimaran	Coconut shell	16～30
Jiangsu-Sensen	Coal quality	8～20
			Jiangsu-Chengsen	Coal quality	8～16
Suzhou-poly-lift source	Coal quality	8～16
			Shandong-nan Ke	Coal quality	8～16
Jiangsu-drop	Coconut shell	8～16
			Hunan Deban	Coal quality	4～8
An Guocheng gloss	Coconut shell					10～20
			Tianjin-Tianyuan	Coal quality	8～16

The average value of the internal pore diameters of the activated carbon is shown below as an average value of 10 pore diameters measured randomly by SEM for the internal cavity of the activated carbon.

The outer package in the following examples is an outer package material, and the inner package is an inner package material.

Experimental example 1

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

dipping 8-16 mesh coconut shell granular activated carbon by using a glucose solution with the mass fraction of 10%, performing suction filtration, and then performing reduced pressure drying at 60 ℃ until the moisture content is less than 2%, thus obtaining the modified activated carbon.

And (3) active carbon characterization detection: the surface morphology of the unmodified activated carbon and the modified activated carbon was tested by SEM, and the detection results are shown in fig. 1 and fig. 2, respectively.

FIG. 1 is a graph showing SEM test results of unmodified activated carbon, wherein the pore diameter of the activated carbon is about 20 microns.

Fig. 2 is a graph showing SEM test results of modified activated carbon, wherein the pore diameter of the activated carbon is about 30 microns, and the pore diameter of the modified activated carbon is changed.

Experimental example 2

Influence of different activated carbon modification modes on ethylene adsorption effect

Calcining: placing the activated carbon in a crucible, placing the crucible in a muffle furnace, setting the required temperature, and calcining for 2-24 h.

Treating with an impregnating solution: and (3) soaking the activated carbon in different solutions completely, filtering, and drying under reduced pressure.

Ethylene embedding ability test: A6X 6 cm packet prepared using a wrapper in a heat sealable filter paper was filled with 2.5 grams of each modified activated carbon. Placing in a 10-wire aluminum foil bag with the length of 450 multiplied by 550cm, filling with 99.99% ethylene gas, sealing, and embedding at normal temperature and pressure for 24h. After removal, each packet was placed in a 1L headspace bottle to test the maximum ethylene release as an ethylene adsorption amount, see Table 2.

TABLE 2 influence of different activated carbon modification modes on ethylene adsorption Effect

Experimental example 3

Effect of different moisture permeability packing materials on ethylene embedding property

(1) Ethylene embedding ability test: the coal active carbon is soaked in 5% sodium dodecyl benzene sulfonate aqueous solution, filtered, placed in a vacuum drying oven, and dried under reduced pressure at 80 ℃ until the water content is less than 1%. A6X 10 cm small bag was prepared from different inner wrappers, 3g of activated carbon was weighed per bag and heat sealed. The small bag is placed in a 250mL high-pressure reaction kettle, 99.99% ethylene gas is introduced to the pressure of 1.5MPa, the reaction is carried out for 24 hours at the temperature of 25 ℃, after the reaction is finished, an air inlet valve is closed, an air outlet valve is opened, and the unadsorbed ethylene is absorbed by potassium permanganate. After removal, each packet was placed in a 1L headspace bottle to test the maximum ethylene release, and the ethylene adsorption was calculated.

(2) The moisture permeability test method comprises the following steps:

the testing method comprises the following steps: GB/T1037-1988 cup method, the detection results are shown in Table 3.

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

Test temperature: 38 ℃ +/-0.5 ℃;

relative humidity: 90% ± 2%.

TABLE 3 Table 3

Example 1

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with the diameter of 180 multiplied by 250mm, the inner package is a small bag with the diameter of 30 multiplied by 30mm, which is heat-sealed by a laminated paper pattern 1, each small bag is provided with 0.1g of 4-8 meshes of granular coal active carbon, and the average value of the inner aperture is 21 microns.

The preparation method comprises the following steps: placing the small bags packaged by the inner package into a closed container, vacuumizing to-0.1 mpa, then filling 99.99% ethylene gas, continuously supplementing ethylene gas, maintaining normal pressure for 16h, taking out the small bags, and packaging with 200 small bags/bag by using an outer package.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 1.5%.

Example 2

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with the diameter of 180 multiplied by 250mm, the inner package is a small bag with the diameter of 30 multiplied by 35mm, which is heat-sealed by a laminated paper pattern 1, and each small bag is provided with 1.0g of 40-80 mesh granular coconut shell activated carbon, and the average value of the inner aperture is 25 microns.

The preparation method comprises the following steps: placing the small bags packaged by the inner package into a closed container, vacuumizing to-0.2 mpa, then filling 99.99% ethylene gas until the pressure is 0.5mpa, maintaining the pressure for 20h, taking out the small bags, and packaging with the outer package, wherein each small bag is 100 small bags.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 8.3%.

Example 3

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with 180X 250mm, the inner package is a small bag with 50X 45mm heat-sealed by a laminated paper pattern 2, and each small bag is provided with 2.5g of 8-16 mesh granular coal active carbon, and the average value of the inner aperture is 23 microns.

The preparation method comprises the following steps: placing the small bags packaged by the inner package into a closed container, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas to the pressure of 3.0mpa, maintaining the pressure for 24h, taking out the small bags, and packaging with the outer package, wherein each small bag is 50 small bags per bag.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 2.5%.

Example 4

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag 130X 180mm, the inner package is a small bag 50X 45mm heat-sealed by a laminated paper pattern 2, each small bag is provided with 2.5g of 200-mesh granular shell activated carbon, and the average value of the inner aperture is 28 microns.

The preparation method comprises the following steps: placing the small bags packaged by the inner package into a closed container, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas, continuously supplementing ethylene gas, maintaining normal pressure for 16h, taking out the small bags, and packaging 20 small bags/each bag by using an outer package.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 2.0%.

Example 5

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with the diameter of 180 multiplied by 250mm, the inner package is a small bag with the diameter of 60 multiplied by 55mm, which is heat-sealed by a laminated paper pattern 3, and each small bag is provided with 10.0g of 8-16 mesh granular coal active carbon, and the average value of the inner aperture is 20 microns.

The preparation method comprises the following steps: placing the small bags packaged by the inner package into a closed container, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas, continuously supplementing ethylene gas, maintaining normal pressure for 16h, taking out the small bags, and packaging 20 small bags/each bag by using an outer package.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 0.4%.

Example 6

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with the diameter of 180 multiplied by 250mm, the inner package is a small package of 30 multiplied by 40mm which is heat-sealed by a water-soluble film sample 1, and each small package is provided with 1.0g of 10-20 mesh granular coconut shell activated carbon, and the average value of the inner aperture is 26 microns.

The preparation method comprises the following steps: placing the small bags packaged by the inner package into a closed container, vacuumizing to-0.1 mpa, then filling 99.99% ethylene gas until the pressure is 2.0mpa, maintaining the pressure for 16h, taking out the small bags, and packaging with the outer package, wherein each small bag is 100 small bags per bag.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 4.0%.

Example 7

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with 200X 300mm, the inner package is a composite non-woven fabric sample 2 heat-seal small package with 30X 50mm, and each small package is provided with 1.5g of 16-30 mesh granular coconut shell activated carbon, and the average value of the inner aperture is 26 microns.

The preparation method comprises the following steps: placing the small bags packaged by the inner package into a closed container, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas until the pressure is 1.8mpa, maintaining the pressure for 20h, taking out the small bags, and packaging with the outer package, wherein each small bag is 100 small bags per bag.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 2.50%.

Example 8

The outer package of the supported ethylene ripening agent is a 12-filament PET/PE bag with 200X 300mm, the inner package is a PE-like 1 heat-seal small bag with 60X 50mm, and each small package is provided with 4.0g of 8-16 mesh granular coconut shell activated carbon, and the average value of the internal pore diameter is 23 microns.

The preparation method comprises the following steps: placing the small bags packaged by the inner package into a closed container, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas to the pressure of 3.0mpa, maintaining the pressure for 24h, taking out the small bags, and packaging with the outer package, wherein each small bag is 50 small bags per bag.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 4.2%.

Example 9

The outer package of the supported ethylene ripening agent is a 12-wire aluminum foil composite bag, 200X 300mm, the inner package is a 1-packet of perforated aluminum foil sample, 60X 45mm, and each packet is provided with 3.50g of 10-20 mesh granular coconut shell activated carbon, and the average value of the inner aperture is 26 microns.

The preparation method comprises the following steps: placing the small bags packaged by the inner package into a closed container, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas to the pressure of 3.0mpa, maintaining the pressure for 24h, taking out the small bags, and packaging with the outer package, wherein each small bag is 50 small bags per bag.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 1.0%.

Example 10

The outer package of the supported ethylene ripening agent is a 14-wire aluminum foil bag with the diameter of 250 multiplied by 300mm, the inner package is a composite non-woven fabric sample 1 heat-sealed package with the diameter of 220 multiplied by 250mm, 1000g of 8-20 mesh granular coal activated carbon is packed in each small package, and the average value of the internal pore diameter is 16 microns.

The preparation method comprises the following steps: placing the small bags packaged by the inner package into a reaction device, filling 99.99% of ethylene gas, continuously supplementing the ethylene gas, maintaining the normal pressure for 24 hours, taking out the small bags, and packaging 1 small bag/each bag by using the outer package.

The maximum ethylene release was tested by placing the packet in a 1 cubic meter account at 2.7%.

Example 11

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with the diameter of 180 multiplied by 250mm, the inner package is a small bag with the diameter of 30 multiplied by 30mm, which is heat-sealed by a laminated paper pattern 1, each small bag is provided with 0.1g of modified activated carbon, and the average value of the inner aperture is 22 microns.

The 4-8 mesh granular coal-based activated carbon of example 1 was modified to prepare a modified activated carbon.

The preparation method comprises the following steps: washing 4-8 mesh granular coal activated carbon with flowing purified water, filtering, and then drying by blowing at 90 ℃ until the water content is less than 2%, thus obtaining the modified activated carbon. Packaging into small bags by using inner package, placing the small bags in a closed container, vacuumizing to-0.1 mpa, then filling 99.99% ethylene gas, continuously supplementing ethylene gas, maintaining normal pressure for 16h, taking out the small bags, and packaging with 200 small bags/each bag by using outer package.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 1.9%.

Example 12

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with the diameter of 180 multiplied by 250mm, the inner package is a small bag with the diameter of 30 multiplied by 35mm, which is heat-sealed by a laminated paper pattern 1, each small bag is provided with 1.0g of modified activated carbon, and the average value of the inner aperture is 32 micrometers.

The granular coconut shell activated carbon of 40-80 meshes in the example 2 is modified to prepare the modified activated carbon.

The preparation method comprises the following steps: adding granular coconut shell activated carbon with 40-80 meshes into 15% sodium dodecyl benzene sulfonate aqueous solution with 1.5 times of volume for soaking, using a suction filtration device for suction filtration, and then drying the activated carbon boiling bed at 70 ℃ until the water content is less than 2%, thus obtaining the modified activated carbon. Packaging into small bags by using an inner package, placing the small bags into a reaction device, vacuumizing to-0.2 mpa, then filling 99.99% ethylene gas until the pressure is 0.5mpa, maintaining the pressure for 20h, taking out the small bags, and packaging with an outer package, wherein each small bag is 100 small bags.

The maximum ethylene release was measured to be 14.5% by placing the packet in a 1L headspace bottle.

Example 13

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with the diameter of 180 multiplied by 250mm, the inner package is a small bag with the diameter of 50 multiplied by 45mm, which is heat-sealed by a laminated paper pattern 2, each small bag is provided with 2.5g of modified activated carbon, and the average value of the inner aperture is 27 microns.

The 8-16 mesh granular coal activated carbon in example 3 was modified to prepare a modified activated carbon.

The preparation method comprises the following steps: adding 8-16 mesh granular coal activated carbon into 2.0 times volume of 10% calcium lignosulfonate aqueous solution, ultrasonically cleaning for 60min, performing suction filtration by using a suction filtration device, and then vacuum drying the activated carbon at 60 ℃ until the water content is less than 2%, thereby preparing the modified activated carbon. Packaging into small bags by using an inner package, placing the small bags into a reaction device, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas to the pressure of 3.0mpa, maintaining the pressure for 24 hours, taking out the small bags, and packaging with an outer package, wherein each small bag is 50 small bags.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 5.1%.

Example 14

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag 130X 180mm, the inner package is a small bag 50X 45mm heat-sealed by a laminated paper pattern 2, each small bag is provided with 2.5g of modified activated carbon, and the average value of the inner aperture is 34 microns.

The 200 mesh granular shell activated carbon in example 4 was modified to obtain a modified activated carbon.

The preparation method comprises the following steps: calcining 200-mesh granular shell activated carbon at 200 ℃ for 24 hours to obtain modified activated carbon. Packaging into small bags by using an inner package, placing the small bags into a reaction device, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas, continuously supplementing ethylene gas, maintaining normal pressure for 16h, taking out the small bags, and packaging with an outer package, wherein each small bag is 20 small bags.

The sachets were placed in 1L headspace bottles to test 6.0% maximum ethylene release.

Example 15

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with the diameter of 180 multiplied by 250mm, the inner package is a small bag with the diameter of 60 multiplied by 55mm heat-sealed by a laminated paper pattern 3, and each small bag is provided with 10.0g of modified activated carbon, and the average value of the inner aperture is 27 microns.

The 8-16 mesh granular coal activated carbon in example 5 was modified to obtain a modified activated carbon.

The preparation method comprises the following steps: calcining the 8-16 mesh granular coal active carbon at 400 ℃ for 10 hours to obtain the modified active carbon. Packaging into small bags by using an inner package, placing the small bags into a reaction device, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas, continuously supplementing ethylene gas, maintaining normal pressure for 16h, taking out the small bags, and packaging with an outer package, wherein each small bag is 20 small bags.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 3.9%.

Example 16

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with the diameter of 180 multiplied by 250mm, the inner package is a small package of 30 multiplied by 40mm which is heat-sealed by a water-soluble film sample 1, each small package is provided with 1.0g of modified activated carbon, and the average value of the inner pore diameter is 34 microns.

The granular coconut shell activated carbon with 10-20 meshes in the example 6 is modified to prepare the modified activated carbon.

The preparation method comprises the following steps: calcining 10-20 mesh granular coconut shell activated carbon at 800 ℃ for 2 hours to obtain modified activated carbon. Packaging into small bags by using an inner package, placing the small bags into a reaction device, vacuumizing to-0.1 mpa, then filling 99.99% ethylene gas until the pressure is 2.0mpa, maintaining the pressure for 16h, taking out the small bags, and packaging with an outer package, wherein each small bag is 100 small bags.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 5.3%.

Example 17

The outer package of the supported ethylene ripening agent is a 10-wire aluminum foil bag with 200X 300mm, the inner package is a composite non-woven fabric sample 2 heat-seal small package with 30X 50mm, each small package is provided with 1.5g of modified activated carbon, and the average value of the inner aperture is 27 microns.

The granular coconut shell activated carbon with 16-30 meshes in the example 7 is modified to prepare the modified activated carbon.

The preparation method comprises the following steps: adding purified water into granular coconut shell active carbon with 16-30 meshes, soaking for 30min at normal temperature, performing suction filtration by using a suction filtration device, and then placing the active carbon into a blast drying box to set the temperature to 90 ℃ and drying until the moisture is less than 2%, thereby preparing the modified active carbon. Packaging into small bags by using an inner package, placing the small bags into a reaction device, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas until the pressure is 1.8mpa, maintaining the pressure for 20h, taking out the small bags, and packaging with an outer package, wherein each small bag is 100 small bags.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 4.6%.

Example 18

The outer package of the supported ethylene ripening agent is a 12-filament PET/PE bag with 200X 300mm, the inner package is a PE-like 1 heat-seal small package with 60X 50mm, each small package is provided with 4.0g of modified activated carbon, and the average value of the inner pore diameter is 30 microns.

The granular coconut shell activated carbon with the particle size of 8-16 meshes in the example 8 is modified to prepare the modified activated carbon.

The preparation method comprises the following steps: adding 8-16 mesh granular coconut shell activated carbon into 10% ammonium chloride aqueous solution with the volume of 5 times, ultrasonically cleaning for 60min, performing suction filtration by using a suction filtration device, and then vacuum drying the activated carbon at the temperature of 60 ℃ until the water content is less than 2%, thereby preparing the modified activated carbon. Packaging into small bags by using an inner package, placing the small bags into a reaction device, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas to the pressure of 3.0mpa, maintaining the pressure for 24 hours, taking out the small bags, and packaging with an outer package, wherein each small bag is 50 small bags.

The sachets were placed in 1L headspace bottles to test 6.1% maximum ethylene release.

Example 19

The outer package of the supported ethylene ripening agent is a 12-wire aluminum foil composite bag with 200X 300mm, the inner package is a perforated aluminum foil sample 1 packet with 60X 45mm, each packet is provided with 3.50g of modified activated carbon, and the average value of the inner aperture is 34 microns.

The granular coconut shell activated carbon of 10-20 meshes in the example 9 is modified to prepare the modified activated carbon.

The preparation method comprises the following steps: adding 10-20 mesh granular coconut shell activated carbon into 5-fold volume of 5% glucose aqueous solution, ultrasonically cleaning for 60min, performing suction filtration by using a suction filtration device, and boiling and drying the activated carbon at 60 ℃ until the water content is less than 1.5%, thereby preparing the modified activated carbon. Packaging into small bags by using an inner package, placing the small bags into a reaction device, vacuumizing to-0.1 mpa, filling 99.99% ethylene gas to the pressure of 3.0mpa, maintaining the pressure for 24 hours, taking out the small bags, and packaging with an outer package, wherein each small bag is 50 small bags.

The sachets were placed in 1L headspace bottles to test a maximum ethylene release of 3.2%.

Example 20

The outer package of the supported ethylene ripening agent is a 14-wire aluminum foil bag with the diameter of 250 multiplied by 300mm, the inner package is a composite non-woven fabric sample 1 heat-sealed package with the diameter of 220 multiplied by 250mm, 1000g of modified activated carbon is packed in each small package, and the average value of the inner aperture is 18 microns.

The 8-20 mesh granular coal activated carbon in example 10 was modified to obtain a modified activated carbon.

The preparation method comprises the following steps: adding 8-20 mesh granular coal activated carbon into 5-time volume of 5% composite alkyl sulfate and 10% ammonium chloride solution water solution, soaking for 30min, suction filtering by a suction filtering device, and drying the activated carbon by blowing at 90 ℃ until the water content is less than 1.0%, thus obtaining the modified activated carbon. Packaging into small bags by using an inner package, placing the small bags into a reaction device, filling 99.99% of ethylene gas, continuously supplementing the ethylene gas, maintaining the normal pressure for 24 hours, taking out the small bags, and packaging with an outer package, wherein each small bag is 1.

The sachets were placed in a 1 cubic meter account for a maximum ethylene release of 3.5%.

Effect example

Application of the above embodiment in preparation of supported ethylene ripening agent

The ripening agents prepared in examples 1 to 20 were first subjected to fruit ripening, and the fruit varieties tested were green ripe banana (green ripe means that ripening conditions have been reached, but the peel was still green) and mango.

The test method comprises the following steps:

ripening bananas: bananas are uniformly grouped, and 3 bananas in each group are parallel; packaging with PVC fresh-keeping bag for banana package, tying, and sheathing with paper box; a bag of ripening agent (without wetting) is placed in parallel in each side opening of the fresh-keeping bag; the ambient temperature is controlled at about 20 ℃, and the relative humidity is kept above 98%; banana status was observed daily and the average ripening period was recorded.

Ripening mango: evenly grouping mangoes, wherein each group is parallel to 3; packaging with a commercial mango carton, and filling water absorbing paper on the upper part, the bottom and the mango space of the mango; a bag of ripening agent (without wetting) is placed in each parallel; the ambient temperature is controlled at about 28 ℃, and the relative humidity is kept above 98%; mango status was observed daily and average ripening period was recorded.

TABLE 4 ripening period with different ripening agents

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As can be seen from Table 4, the ripening agent of the present utility model was applied to mangoes and bananas for a ripening period of 2 to 4 days. The ripening agent prepared by the modified activated carbon has better ripening effect than the ripening agent prepared by the unmodified activated carbon under the same preparation condition.

(II) commercial ripening agent and use of example 3 to prepare ripening agent

Test method

Green ripe small table mango which is not subjected to ripening treatment is purchased in the fruit wholesale market of Jinan dyke, fresh mango which is free of diseases and damage is selected, and the mango is randomly divided into 9 groups of three parallel treatments.

Treatment 1: after the ripening agent prepared in the embodiment 3 is opened in the outer package, the ripening agent is quickly placed in clear water to be soaked for 15 seconds, the medicine bag is taken and placed above mangoes, and peripheral paper is quickly paved and piled up;

treatment 2: after the ripening agent prepared in the embodiment 3 is opened in the outer package, the medicine package is placed above the mangoes, and the peripheral paper is paved and piled up rapidly;

treatment 3: after the commercial mango ripening agent (3.0 g per small package and 20% of ethephon content) is opened out of the outer package, the medicine bag is taken and placed above the mango, and the surrounding paper is paved and piled up rapidly.

The temperature is kept at 28 ℃ and the relative humidity is more than 90 percent. And (5) observing the appearance of the mangoes every day, and determining the peel yellowing index according to the mango color change condition.

(2) Statistical analysis of data

According to the investigation result, calculating an experimental result by adopting Excel and PASS data processing software, and respectively solving the yellowing index of the heating and pericarp of each treatment.

Peel yellowing index:

the peel color is classified into 5 grades:

level 0: all green;

stage 1: slightly yellowing (25%) at the pedicel;

2 stages: the parts except the pedicel are partially yellowing (25% -50%);

3 stages: about 50% -75% yellowing exists on the surface of the pericarp;

4 stages: the peel turned yellow mostly (75%).

(3) Experimental results and analysis

The commercial mango ripening agent and the ripening agent prepared in example 3 treated mango 3-3.5 turned yellow all, and the mango used directly turned yellow all to ripen in 2.5-3 days, and the experimental results are shown in table 5.

TABLE 5 influence of different treatments on mango indices

The ripening agent prepared in example 3 was free of risk of ethephon leakage relative to commercially available mango ripening agents, without phytotoxicity for each treatment. Commercial mango ripeners and wet-out the ripener treated mangoes prepared in example 3 were substantially all turned yellow in 3-3.5 d. The mangoes treated with the ripening agent prepared in example 3, which was used directly, were all turned yellow to ripen in 2.5-3 days. The ripening period is shorter and there is no risk of ethephon leakage compared to commercial mango ripening agents.

The ripening agent prepared by the method has the advantages of wide sources of raw materials, low cost, easy obtainment and convenient use, and particularly has better effect on the ripening agent prepared by the modified activated carbon, and the ripening agent prepared by the method has no ethephon and no risk of ethephon leakage. The preparation method has the advantages of no chemical reaction during use, direct contact with fruits and vegetables, no accumulation, no peculiar smell, no residue, environmental friendliness, simple preparation method and low cost.

Claims (10)

1. A supported ethylene ripening agent is characterized by comprising activated carbon adsorbed with ethylene and a packing material.

2. The supported ethylene ripening agent as claimed in claim 1, wherein the mass percentage of the activated carbon adsorbed ethylene is 0.4-15%;

preferably, the mass percentage of the activated carbon to adsorb ethylene is 1-15%.

3. The supported ethylene ripening agent as claimed in claim 1, wherein the packing material comprises an inner packing material, the moisture permeability of the inner packing material is in the range of 5-3000 g/m ² .24h；

Preferably, the moisture permeability of the inner wrapping material is in the range of 10-100 g/m ² .24h；

Preferably, the inner packaging material comprises a water-soluble film, a coated paper, a composite non-woven fabric, a plastic film, an aluminum foil and filter paper;

preferably, the packaging material further comprises an outer packaging material, and the outer packaging material is impermeable to ethylene;

preferably, the outer coating material comprises aluminum foil, aluminum foil composite film and PET/PE composite film.

4. The supported ethylene ripening agent of claim 3, wherein the packing amount of the activated carbon of the inner packing material of the ripening agent is more than 0.1g per pack;

preferably, the packing amount of the activated carbon of the inner packing material is 0.1-1000 g per pack;

preferably, the packing amount of the activated carbon of the inner packing material is 0.5-10 g per pack.

5. The supported ethylene ripener of claim 1, wherein the activated carbon has an internal pore size of 16 to 40 microns;

preferably, the internal pore diameter of the activated carbon is 25-40 microns;

preferably, the activated carbon is in the form of powder or granules;

preferably, the activated carbon is granular;

preferably, the diameter of the activated carbon particles is 4-50 meshes;

preferably, the diameter of the activated carbon particles is 5-25 meshes;

preferably, the activated carbon comprises one or more than two of coal activated carbon, coconut shell activated carbon, fruit shell activated carbon and wood activated carbon;

preferably, the activated carbon is coal activated carbon or coconut activated carbon.

6. The supported ethylene ripener of claim 1, wherein the activated carbon is a modified activated carbon;

preferably, the preparation method I of the modified activated carbon comprises the following steps:

washing the activated carbon, and drying to obtain modified activated carbon;

preferably, the washing mode comprises one or more than two of ultrasonic cleaning, dipping and flushing;

the washing liquid comprises water and/or an aqueous solution;

preferably, the solute of the aqueous solution is a surfactant and/or a water absorbing component;

the surfactant comprises one or more than two of dodecyl trimethyl ammonium chloride, sodium lignin sulfonate, calcium lignin sulfonate, dibutyl sodium naphthalene sulfonate formaldehyde condensate, sodium hexametaphosphate, sodium tripolyphosphate, alkyl sulfate, dodecyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl succinic acid sulfonate and Chinese honeylocust fruit powder;

the water absorption component comprises one or more than two of magnesium sulfate, calcium chloride, glucose, sodium sulfate and ammonium chloride;

preferably, the drying mode comprises vacuum drying, forced air drying and ebullated bed drying.

7. The supported ethylene ripener of claim 6, wherein the modified activated carbon is prepared by a process ii comprising the steps of:

calcining the activated carbon at the temperature of 200-800 ℃ for 2-24 hours to obtain the modified activated carbon.

8. The method for preparing the supported ethylene ripening agent as claimed in any one of claims 1 to 7, comprising the steps of:

(1) Quantitatively packaging the activated carbon with an inner packaging material, and sealing to obtain an activated carbon package;

(2) Placing the activated carbon obtained in the step (1) in a closed container, and filling ethylene gas for embedding for 0.5-24 h, wherein the embedding mode is normal-pressure embedding or high-pressure embedding; the high-pressure embedding pressure is 0.5-3 mpa, and the activated carbon bag adsorbed with ethylene is prepared, namely the supported ethylene ripening agent;

preferably, in the step (2), the activated carbon bag having absorbed ethylene is packaged by an outer wrapping material which does not penetrate ethylene, and is sealed.

9. Use of the supported ethylene ripening agent of any one of claims 1 to 7 in the field of ripening;

preferably, the application of the supported ethylene ripening agent in fruit and vegetable ripening;

preferably, the fruits and vegetables comprise mangoes and bananas;

preferably, the dosage of the load type ethylene ripening agent is 0.01-5 g based on the weight of the active carbon per kilogram of mango; the dosage of the supported ethylene ripening agent is 0.001-2 g per kilogram of banana based on the weight of active carbon.

10. The method of using a supported ethylene ripener of any one of claims 1-7, comprising the steps of:

directly placing the load type ethylene ripening agent into a fruit and vegetable package, and managing according to conventional ripening temperature and humidity conditions;

or, the load type ethylene ripening agent is soaked in water, taken out and then directly put in the fruit and vegetable package, and is managed according to the conventional ripening temperature and humidity conditions.

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