CN108719456A - A kind of fruit and vegetable fresh-keeping agent and its preparation method and application - Google Patents
A kind of fruit and vegetable fresh-keeping agent and its preparation method and application Download PDFInfo
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- CN108719456A CN108719456A CN201810440220.4A CN201810440220A CN108719456A CN 108719456 A CN108719456 A CN 108719456A CN 201810440220 A CN201810440220 A CN 201810440220A CN 108719456 A CN108719456 A CN 108719456A
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- fruit
- keeping agent
- vegetable fresh
- attapulgite clay
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/154—Organic compounds; Microorganisms; Enzymes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Storage Of Fruits Or Vegetables (AREA)
- Storage Of Harvested Produce (AREA)
Abstract
The invention discloses a kind of fruit and vegetable fresh-keeping agent, which is attapulgite clay@metal-organic framework composite materials（Referred to as：ATP@MOF）；Metal-organic framework is hydroxylating Al2(OH)2(C8O6H4).The invention also discloses the preparation method and application of the fruit and vegetable fresh-keeping agent.Antistaling agent of the present invention can not only remove the ethylene gas for promoting fruits and vegetables aging in storing environment, the hydrogen sulfide gas of mechanical damage wound release, also have effects that suppression sterilizing living.
Description
Technical field
The invention belongs to gardening product post-processing technical field, it is related to a kind of fruit and vegetable fresh-keeping agent and preparation method thereof and answers
With.
Background technology
China is a large agricultural country, and fruits and vegetables market also becomes increasingly prosperous, and fruits and vegetables industry is also gradually being grown, but China is annual
Because fresh-keeping measure is not in place low with preservation technology level, loss is up to 25%~30% after fruit is adopted, and vegetables are then up to 30%~40%, often
Year, there are about more than 100,000,000 tons of fruits and vegetables to rot, and for economic loss up to 100,000,000,000 yuan, the fruits and vegetables industry in China is badly in need of escorting for fresh-keeping industry.
It is common fresh-keeping means by controlling ethylene contents in fruit vegetables storing environment and sterilizing.Using potassium permanganate as generation
The oxidized form adsorbent of table shows good effect, but its chemical characteristic and safeguard procedures pole not in place when removing ethylene
Fruits and vegetables easy to pollute, use are extremely inconvenient.Belong to physical absorbent by the porous structure substance of representative of activated carbon, only by point
Faint active force adsorbs ethylene molecule between son, and adsorption efficiency and adsorption capacity are relatively low.Gold with periodic network structure
Category-organic frame compound porosity and extra specific surface area, abundant topology with superelevation compared with traditional sorbing material
The unique advantages such as structure, special metal center and adjustable, Scalability, show in the absorption of low-carbon the hydrocarbon component
Excellent performance, but it has the shortcomings that meeting water-bound collapses, and can cause absorption property to drastically reduce again.With layer chain structure
Attapulgite clay also have unique performance in terms of gas absorption and sterilizing, and its stable structure.The two is combined,
Using attapulgite clay as supporter, metal-organic framework compound is grown in its surface in situ, it is steady to prepare structure
Composite material fixed, absorption property is excellent is applied to the gas in absorption fruit and vegetable storage and transportation environment and sterilizing, will effectively reduce China
The loss of fruit and vegetable storage and transportation link ensures storing phase fruit-vegetable quality, lays the foundation for China's gardening product Opening International Market.
Invention content
The object of the present invention is to provide it is a kind of remove ethylene, hydrogen sulfide gas and with antibacterial deactivation fruits and vegetables guarantor
Fresh dose and its preparation method and application.
A kind of fruit and vegetable fresh-keeping agent, it is characterised in that the fruit and vegetable fresh-keeping agent is that attapulgite clay@metal-organic frameworks are compound
Material（Referred to as：ATP@MOF）；The metal-organic framework is hydroxylating Al2(OH)2(C8O6H4)。
The pore size of the fruit and vegetable fresh-keeping agent is 6.0 × 6.0, Kong Rongwei, 0.40~0.50 cm3/ g, grain size are
10~30 μm, specific surface area is 800~1200 m2/g。
The preparation method of fruit and vegetable fresh-keeping agent as described above, it is characterised in that the specific steps are：
1）By Al (NO3)3·9H2O, 2,5- dihydric para-phthalic acids（DHTA）It is dispersed in N, N- diformazans with attapulgite clay
Base formamide（DMF）In；
2）Be uniformly dispersed be placed on 100~140 DEG C react 18~24 hours；
3）It is cooled to room temperature after reaction, removes supernatant, collect the crystal of deposition, product uses N, N- dimethyl formyls successively
3~4 h are dried after amine, ethyl alcohol, distillation water washing at 120 DEG C up to fruit and vegetable fresh-keeping agent.
Al (the NO3)3·9H2O, 2,5- dihydric para-phthalic acids, attapulgite clay, N,N-dimethylformamide
Mass ratio be 20~39:10~21:40~70:900.
The attapulgite clay（ATP）It is purified according to purifying known in field, acid activation, Homogenization
Disperse with brilliant beam.
The application of fruit and vegetable fresh-keeping agent as described above, it is characterised in that one layer of amylan is first applied in universal storing carton,
Then fruit and vegetable fresh-keeping agent is sprayed on its surface.
The quantity for spray of the fruit and vegetable fresh-keeping agent is 1~2 g/m2。
Metal-is had machine frame by fruit and vegetable fresh-keeping agent of the present invention using attapulgite clay as matrix, by situ synthesis
Frame compound is assembled in attapulgite clay surface.
Fruit and vegetable fresh-keeping agent of the present invention mainly utilizes attapulgite clay layer chain structure and hydroxylating Al2(OH)2
(C8O6H4) porous performance, the substance of both structures is to the ethylene gas of release during fruit and vegetable storage and transportation with strong adsorption energy
Power, in 293 K, 105 Pa, the fruit and vegetable fresh-keeping agent is 5.0~5.8 mol/kg to the adsorption capacity of ethylene, can effectively reduce storage
The ethylene contents in environment are transported, the fruits and vegetables climacteric time are postponed, to realize fresh-keeping purpose.
Fruit and vegetable fresh-keeping agent of the present invention can also effectively adsorb the wound generated by mechanical damage in fruit and vegetable picking handling process
The hydrogen sulfide gas of mouth release, in 293 K, 105 Pa, the fruit and vegetable fresh-keeping agent is 2.0~2.6 to hydrogen sulfide adsorption capacity
Mol/kg, so as to slow down the rotten progress of fruits and vegetables.
Fruit and vegetable fresh-keeping agent of the present invention is to form π networks by unsatuated metal site and ethylene to the adsorption mechanism of ethylene
Cooperation is used and π ... pi accumulations act synergistically and realize the relatively strong absorption to ethylene molecule.
The hydroxylating Al2(OH)2(C8O6H4) in the presence of water structure easily collapse, cause its absorption property to decline, and it is recessed
Convex stick stone clay moisture-stable, therefore using attapulgite clay as supporter, to inhibit hydroxylating Al2(OH)2(C8O6H4) meet water
Structural collapse problem.
Fruit and vegetable fresh-keeping agent of the present invention also uses characteristic of the attapulgite clay with sterilizing, disinfecting power itself,
Inhibit erosion of the mould to fruits and vegetables in transporting procedures, realizes fresh-keeping purpose.
Specific implementation mode
Embodiment 1
Attapulgite clay purifying and brilliant beam dispersion are carried out using conventional method purifying, acid activation, Homogenization, it is spare.
Measure 94.7 mL N,N-dimethylformamides（DMF）In the flat single-necked flasks of 250mL, under stirring successively
2.0 grams of Al (NO are added3)3·9H2O, 1.0 grams of 2,5- dihydric para-phthalic acids（DHTA）With 7.0 grams of attapulgite clay, add
It is dispersed with stirring 10min after material, is placed in 120 DEG C of constant temperature ovens and is reacted 18 hours with tinfoil paper sealing bottleneck.Reaction terminates
Afterwards, naturally cool to room temperature, incline supernatant, product successively use n,N-Dimethylformamide, ethyl alcohol, distillation water washing after
120 DEG C of 4 h of drying, obtained solid powder is antistaling agent, and it is 850 m to test its specific surface area20.50 cm of/g, Kong Rongwei3/ g exists
Ethylene absorption capacity is 5.3 mol/kg when 293 K, 105 Pa, and hydrogen sulfide adsorption capacity is 2.2 mol/kg.
One layer of amylan is brushed in fruits and vegetables transhipment carton, solid powder antistaling agent is then sprayed on its surface, controls it
Quantity for spray is 1~2 g/m2To get fruit and vegetable storage and transportation antistaling box.
Embodiment 2
By spare after the purifying of 1 the method for embodiment, dispersed attapulgite clay.
Measure 94.7 mL N,N-dimethylformamides（DMF）In the flat single-necked flasks of 250mL, under stirring successively
2.6 grams of Al (NO are added3)3·9H2O, 1.4 grams of 2,5- dihydric para-phthalic acids（DHTA）With 6.0 grams of attapulgite clay, add
Ultrasonic disperse 20min after material is placed in 140 DEG C of constant temperature ovens with tinfoil paper sealing bottleneck and is reacted 20 hours.Reaction terminates
Afterwards, naturally cool to room temperature, incline supernatant, product successively use n,N-Dimethylformamide, ethyl alcohol, distillation water washing after
120 DEG C of 4 h of drying, obtained solid powder is antistaling agent, and it is 1060 m to test its specific surface area20.46 cm of/g, Kong Rongwei3/ g exists
Ethylene absorption capacity is 5.7 mol/kg when 293 K, 105 Pa, and hydrogen sulfide adsorption capacity is 2.5 mol/kg.
The antistaling agent that embodiment 2 is prepared is sprayed on carton inner wall surface by 1 the method for embodiment, fruits and vegetables is made and protects
Fresh case.
Embodiment 3
By spare after the purifying of 1 the method for embodiment, dispersed attapulgite clay.
Measure 94.7 mL N,N-dimethylformamides（DMF）In the flat single-necked flasks of 250mL, under stirring successively
3.9 grams of Al (NO are added3)3·9H2O, 2.1 grams of 2,5- dihydric para-phthalic acids（DHTA）With 4.0 grams of attapulgite clay, add
Ultrasonic disperse 20min after material is placed in 100 DEG C of constant temperature ovens with tinfoil paper sealing bottleneck and is reacted 24 hours.Reaction terminates
Afterwards, naturally cool to room temperature, incline supernatant, product successively use n,N-Dimethylformamide, ethyl alcohol, distillation water washing after
120 DEG C of 3 h of drying, obtained solid powder is antistaling agent, and it is 1180 m to test its specific surface area20.41 cm of/g, Kong Rongwei3/ g exists
Ethylene absorption capacity is 5.1 mol/kg when 293 K, 105 Pa, and hydrogen sulfide adsorption capacity is 2.0 mol/kg.
The antistaling agent that embodiment 3 is prepared is sprayed on carton inner wall surface by 1 the method for embodiment, fruits and vegetables is made and protects
Fresh case.
Claims (7)
1. a kind of fruit and vegetable fresh-keeping agent, it is characterised in that the fruit and vegetable fresh-keeping agent is attapulgite clay@metal-organic framework composite woods
Material；The metal-organic framework is hydroxylating Al2(OH)2(C8O6H4)。
2. fruit and vegetable fresh-keeping agent as described in claim 1, it is characterised in that the pore size of the fruit and vegetable fresh-keeping agent be 6.0 ×
6.0, Kong Rongwei 0.40~0.50 cm3/ g, grain size are 10~30 μm, and specific surface area is 800~1200 m2/g。
3. the preparation method of fruit and vegetable fresh-keeping agent as claimed in claim 1 or 2, it is characterised in that the specific steps are：
1）By Al (NO3)3·9H2O, 2,5- dihydric para-phthalic acids and attapulgite clay are dispersed in N, N- dimethyl formyls
In amine；
2）Be uniformly dispersed be placed on 100~140 DEG C react 18~24 hours；
3）It is cooled to room temperature after reaction, removes supernatant, collect the crystal of deposition, product uses N, N- dimethyl formyls successively
3~4 h are dried after amine, ethyl alcohol, distillation water washing at 120 DEG C up to fruit and vegetable fresh-keeping agent.
4. preparation method as claimed in claim 3, it is characterised in that the Al (NO3)3·9H2O, 2,5- dihydroxy is to benzene two
Formic acid, attapulgite clay, N,N-dimethylformamide mass ratio be 20~39:10~21:40~70:900.
5. preparation method as claimed in claim 3, it is characterised in that the attapulgite clay is according to known in field
Purifying, acid activation, Homogenization carry out purifying and brilliant beam dispersion.
6. the application of fruit and vegetable fresh-keeping agent as claimed in claim 1 or 2, it is characterised in that first apply one layer in universal storing carton
Then fruit and vegetable fresh-keeping agent is sprayed on its surface by amylan.
7. application as claimed in claim 6, it is characterised in that the quantity for spray of the fruit and vegetable fresh-keeping agent is 1~2 g/m2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810440220.4A CN108719456A (en) | 2018-05-10 | 2018-05-10 | A kind of fruit and vegetable fresh-keeping agent and its preparation method and application |
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| CN201810440220.4A CN108719456A (en) | 2018-05-10 | 2018-05-10 | A kind of fruit and vegetable fresh-keeping agent and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110013879A (en) * | 2019-04-29 | 2019-07-16 | 西北师范大学 | A kind of MIL-101 (Fe) load palygorskite photochemical catalyst and preparation method thereof |
| CN112998068A (en) * | 2021-03-17 | 2021-06-22 | 星探桔(杭州)网络科技有限公司 | Fresh-keeping method of bamboo shoots |
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| CN102744105A (en) * | 2011-04-18 | 2012-10-24 | 韩国化学研究院 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
| CN103694260A (en) * | 2013-12-02 | 2014-04-02 | 南京工业大学 | High-stability metal organic framework hybrid material, preparation method and application thereof |
| JP2016094220A (en) * | 2014-11-13 | 2016-05-26 | デンカ株式会社 | Microwave absorbing package, container for microwave oven cooking having the same, and cooking method |
| CN107074429A (en) * | 2014-09-05 | 2017-08-18 | 巴斯夫公司 | Sorbent material for extending agricultural product (produce) storage life |
| CN107307069A (en) * | 2016-04-27 | 2017-11-03 | 上海鲜锐生物科技有限公司 | 1- methyl cyclopropenes preparation and preparation and application for fruits and vegetables flower freshness |
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2018
- 2018-05-10 CN CN201810440220.4A patent/CN108719456A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248034A (en) * | 2005-08-22 | 2008-08-20 | 巴斯夫欧洲公司 | Method for producing organometallic framework materials containing main group metal ions |
| CN102744105A (en) * | 2011-04-18 | 2012-10-24 | 韩国化学研究院 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
| CN103694260A (en) * | 2013-12-02 | 2014-04-02 | 南京工业大学 | High-stability metal organic framework hybrid material, preparation method and application thereof |
| CN107074429A (en) * | 2014-09-05 | 2017-08-18 | 巴斯夫公司 | Sorbent material for extending agricultural product (produce) storage life |
| JP2016094220A (en) * | 2014-11-13 | 2016-05-26 | デンカ株式会社 | Microwave absorbing package, container for microwave oven cooking having the same, and cooking method |
| CN107307069A (en) * | 2016-04-27 | 2017-11-03 | 上海鲜锐生物科技有限公司 | 1- methyl cyclopropenes preparation and preparation and application for fruits and vegetables flower freshness |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110013879A (en) * | 2019-04-29 | 2019-07-16 | 西北师范大学 | A kind of MIL-101 (Fe) load palygorskite photochemical catalyst and preparation method thereof |
| CN112998068A (en) * | 2021-03-17 | 2021-06-22 | 星探桔(杭州)网络科技有限公司 | Fresh-keeping method of bamboo shoots |
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Application publication date: 20181102 |