CN101513604B - Improved copper ethylene absorbent and preparation method thereof - Google Patents
Improved copper ethylene absorbent and preparation method thereof Download PDFInfo
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- CN101513604B CN101513604B CN2009100962227A CN200910096222A CN101513604B CN 101513604 B CN101513604 B CN 101513604B CN 2009100962227 A CN2009100962227 A CN 2009100962227A CN 200910096222 A CN200910096222 A CN 200910096222A CN 101513604 B CN101513604 B CN 101513604B
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Abstract
The invention discloses an improved copper ethylene absorbent, prepared by supporting the metal copper on the carrier, comprising, based on the weight percentage, 0.1-6% of copper and 94-99.9% of the carrier, wherein the carrier is one of active carbon, zeolite, diatomite, molecular sieve and alumina. The improved copper ethylene absorbent has good fresh-keeping effect, long usage period, no poison and little effect by the temperature and humidity, can rapidly absorb the organic gas such as ethylene, methane and the like and has big adsorption quantity, and can be recycled and reused with simple recovery method. The invention also discloses a preparation method of the improved copper ethylene absorbent, having simple operation and being suitable for the industrial production.
Description
Technical field
The present invention relates to fruits and vegetables and flower freshness technology, be specifically related to a kind of improved copper ethylene absorbent that is used for fruits and vegetables and flower freshness and preparation method thereof.
Background technology
Fruit, vegetables and flowers are being adopted the back owing to be subjected to the influence of factors such as physics, physiology and pathology, and its output and quality all are subjected to serious loss.Show that according to the FAO statistics developed country is because the postharvest fruit and vegetable preservation technique is fairly perfect, and its product loss rate only is 5%, and developing country is 20%～30% in the world, China's postharvest fruit and vegetable is lost in about 20%.Flower freshness also is crucial work in the commodity production of flowers and plants, storing and circulation.
Ethene is the very little gas of a kind of molecule, can be produced by plant usually, and the ethene of low concentration is to plant or the fruits and vegetables after gathering, flowers just have very big spread effect, are a kind of plant hormone.Ethene is to produce adverse influence to the effect overwhelming majority of fruits and vegetables, flower characteristic, for example promotes that fruits and vegetables are aging, blade yellow, fruit rot etc.; It is positive having only seldom the example of counting to accelerate the ripening as fruit, so ethene is normally harmful on fruits and vegetables, flowers fresh-keeping.
Because ethene is a kind of gas, be easy to transmit everywhere, therefore make ethene more extensive to the injury of fruits and vegetables, flowers, will note the strick precaution to ethene on the storage fresh-keeping of fruits and vegetables, flowers, scientist has studied many methods and has reduced the injury of ethene to fruits and vegetables, flowers for this reason.
One of method of reduction commonly used at present or elimination ethene is for adopting ethylene absorbent, it is divided into physical absorbent and chemical reactor two big classes, wherein physical absorbent mainly comprises the materials such as active carbon, mineral dust, molecular sieve and synthetic resin with trickle loose structure, this class adsorbent is to the ethene non-selectivity, and the rate of adsorption is fast, and temperature influence is less; And, belong to weak absorption because ethene belongs to the difficult gas that is adsorbed, and physical absorbent only relies on the molecular separating force effect to the absorption of ethylene molecule, be easy to desorption.
The ethylene absorbent that is widely used in the chemical reactor is potassium permanganate to be loaded on the carriers such as active carbon, aluminium oxide, molecular sieve make mostly.Though this class absorbent is long service time, result of use is better, because potassium permanganate has certain toxicity, leaks easily in the use, can bring serious food-safety problem.In addition, the absorbent of the type can not reclaim and recycle, and manganese element wherein also can cause environmental pollution.
Current, metal is loaded to technology on the porous carrier generally as the catalyst of preparation olefinic polyreaction, but this technology is applied to the preparation of fruits and vegetables and flower antistaling agent, yet there are no all at home and abroad in report.
Summary of the invention
The invention provides a kind of improved copper ethylene absorbent and preparation method thereof, utilize avirulent metallic copper (Cu) to replace the potassium permanganate in the conventional method to be carried on the porous carrier, make be subjected to humidity effect little, can absorb ethene and the big ethylene absorbent of adsorption capacity rapidly.
A kind of improved copper ethylene absorbent is carried on the carrier by metallic copper and makes, and wherein metallic copper is inner surface and the outer surface that graininess is scattered in carrier.
Consider that from the adsorption capacity of absorbent ethylene absorbent of the present invention preferably is made up of following components in weight percentage:
Metallic copper 0.1%～6%
Carrier 94%～99.9%.
Because the content of Cu is too low, can reduce the adsorption capacity of absorbent, and the content of Cu is too high, metallic copper particle can flock together, and reduces the surface area of metallic copper, thereby reduces the adsorption capacity of absorbent.
The preparation method of improved copper ethylene absorbent of the present invention may further comprise the steps:
(1) adopt equi-volume impregnating, mantoquita is dissolved in is mixed with maceration extract in the deionized water, the carrier with activation flooded 5 hours in maceration extract at least then, obtained sample;
(2) with the sample of step (1) gained in 80～110 ℃ of dryings 3～5 hours, again in 300～400 ℃ of roastings 1～2 hour, be reductase 12～3 hour in the hydrogen of 30～60ml/min in 300～400 ℃, flow velocity then, promptly make improved copper ethylene absorbent.
Described mantoquita is Cu (NO
3)
2, CuCl
2In one or both, can also adopt the crystalline hydrate of above-mentioned mantoquita, such mantoquita can not influence the activity of absorbent, and need use the deionized water cyclic washing after dipping, avoids washing away a part of attached to the Cu on the carrier
2+, the active component Cu in the absorbent of final preparation is reduced, reduce the ability of ethylene adsorption.
Described carrier is a kind of in active carbon, zeolite, diatomite, molecular sieve, the aluminium oxide.Active carbon, zeolite, diatomite, molecular sieve and aluminium oxide all can be selected conventional commercially available prod for use, as select resistant to elevated temperatures molecular sieve 13X type molecular sieve, HY (Si/Al=2.8) type molecular sieve, NaY (Si/Al=2.7) type molecular sieve, γ-Al for use
2O
3All can reach effect preferably in carrier.These carriers are owing to all have a very big specific area, and be simple and easy to, metallic copper is loaded to the ability that can effectively improve ethylene adsorption on these carriers.
Select different carriers, bigger to the influence of absorbent of the present invention, under the identical load amount, big when the adsorption capacity of ethene adopts active carbon to make carrier when selecting zeolite, diatomite, aluminium oxide etc. to make carrier; Zeolite is during as carrier (wherein the Cu weight percentage is 2%), the 1g absorbent to the adsorption capacity of ethene probably at 2100 μ l.
In the step (1), when described carrier was active carbon, its activation method was: be that 30% aqueous solution of nitric acid refluxed 4 hours in 60 ℃ of water-baths with the active carbon mass percentage concentration, spend deionised water at last to neutral, promptly get the active carbon that activates after the drying; Roasting in the step (2) is preferably carried out in nitrogen environment, and is oxidized and make metallic particles assemble to avoid active carbon, reduces the adsorption capacity of absorbent to ethene.
When described carrier is aluminium oxide, diatomite, zeolite or molecular sieve, its activation method is: with after aluminium oxide, diatomite, zeolite or the molecular sieve drying in 200～500 ℃ of roastings 2～3 hours, pulverize the back and cross 20～60 mesh sieves, tail over and be granularity 20～60 purpose activated carriers.The carrier granular size is bigger to the load effect influence of metallic copper, and load effect was better when granularity was 20～60 orders.
Described equi-volume impregnating refers to measure in advance the saturated absorption ability of a certain amount of carrier to solution, adds the method that just in time makes the required solution amount of carrier thorough impregnation (being the saturated pickup of carrier) then.This method can be saved the step of filtering unnecessary maceration extract, is convenient to control the content of activity component metal copper in the absorbent, saves active component.During concrete operations, weighing 1g carrier flooded 5 hours in excessive maceration extract at least in advance, behind the suction filtration, blot the maceration extract on wet basis surface with filter paper, wet basis is weighed, and the weight difference of wet basis and carrier is the saturated pickup of carrier, then, can take by weighing a certain amount of carrier, add maceration extract with reference to above saturated pickup and promptly can reach incipient impregnation.
The present invention has following advantage:
(1) ethylene absorbent good refreshing effect of the present invention, life cycle long, nontoxic, influenced not quite by temperature humidity, can absorb organic gas such as ethene, methane rapidly, and adsorption capacity big (the potassium permanganate load capacity is 5% absorbent on the 〉=alumina support), active carbon is during as carrier (wherein the Cu weight percentage is 2%), 1 gram absorbent to the saturated adsorption capacity of ethene greatly about 1000～1200 μ l.
(2) adopt active carbon, zeolite, molecular sieve, diatomite, aluminium oxide all can be recycled among the present invention, and recovery method is simple as the absorbent of carrier.Its recovery method is: by desorption, as temperature-switching method, transformation method, inert gas purge vaporizing extract process, displacement gas sweeping method; Adopt active carbon as the absorbent of carrier recoverable metal also in addition, detailed process: high-temperature process can obtain the metallic copper oxide with the active carbon high-temp oxidation, then through a series of handle mantoquita.
(3) the material used in the present invention material that is reasonable price and is easy to get, cost is low; With respect to gas impregnated method, the equi-volume impregnating of employing is simple to operate, need not special equipment, and the distribution of metallic copper is also comparatively even in the absorbent that makes.
Description of drawings
Fig. 1 is that the active carbon of improved copper ethylene absorbent, untreated active carbon and activation of embodiment 1 preparation is to the adsorption penetration curve of ethene;
Fig. 2 is that the active carbon of improved copper ethylene absorbent, untreated active carbon and activation of embodiment 2 preparation is to the adsorption penetration curve of ethene;
Fig. 3 is that the active carbon of improved copper ethylene absorbent, untreated active carbon and activation of embodiment 3 preparation is to the adsorption penetration curve of ethene;
Fig. 4 is relative humidity 0% and 90% o'clock, and the improved copper ethylene absorbent of embodiment 1 preparation is to the adsorption penetration curve of ethene;
Fig. 5 is the adsorption penetration curve of the improved copper ethylene absorbent of embodiment 4 preparations to ethene;
Fig. 6 is the adsorption penetration curve of the improved copper ethylene absorbent of embodiment 5 preparations to ethene;
Fig. 7 is the adsorption penetration curve of the improved copper ethylene absorbent of embodiment 6 preparations to ethene;
Fig. 8 is the adsorption penetration curve of the improved copper ethylene absorbent of embodiment 7 preparations to ethene.
The specific embodiment
The activation method of used carrier is as follows among the embodiment 1～7:
The activation method of active carbon is: be that 30% aqueous solution of nitric acid refluxed 4 hours in 60 ℃ of water-baths with the active carbon mass percentage concentration, spend deionised water at last to neutral, promptly get the active carbon that activates after the drying.
The activation method of aluminium oxide, diatomite, zeolite or molecular sieve is: with after aluminium oxide, diatomite, zeolite or the molecular sieve drying in 350 ℃ of roastings 2.5 hours, pulverize the back and cross 40 mesh sieves, tailing over and being granularity is 40 purpose activated alumina, diatomite, zeolite or molecular sieve.
(1) adopts equi-volume impregnating, with 0.1336gCuCl
22H
2O is dissolved in the 7.5ml deionized water and is mixed with maceration extract, and the active carbon with the 5g activation flooded in maceration extract 6 hours then, obtained sample;
(2) with the sample of step (1) gained in 100 ℃ of baking ovens dry 4 hours, go to again Muffle furnace in nitrogen environment in 400 ℃ of roastings 1 hour, placing 400 ℃, hydrogen flow rate then is the reduction tube reductase 12 hour of 40ml/min, promptly get improved copper ethylene absorbent, wherein the Cu percentage by weight is 1%, and the active carbon percentage by weight is 99%.
This absorbent is seen Fig. 1 to the adsorption penetration ability of ethene, test method is: under the room temperature normal pressure, with ethylene concentration is that the air of 300ppm feeds respectively in the active carbon of the improved copper ethylene absorbent of equivalent, untreated active carbon and activation, gas flow rate is 32ml/min, detects the concentration of ethene in the tail gas.
The active carbon of the above-mentioned improved copper ethylene absorbent of equivalent, untreated active carbon, activation is put into three warehouses that store the equivalent tomato respectively, room temperature places that observed result is after 7 days: the good fruit rate of placing tomato in the warehouse of improved copper ethylene absorbent is 95.6%, free from extraneous odour; The good fruit rate of placing tomato in the warehouse of untreated active carbon is 20.1%, and obvious peculiar smell is arranged; The good fruit rate of tomato is 35.2% in the warehouse of the active carbon of placement activation, and peculiar smell is arranged.
(1) adopts equi-volume impregnating, with 0.2671gCuCl
22H
2O is dissolved in the 7.5ml deionized water and is mixed with maceration extract, and the active carbon with the 5g activation flooded in maceration extract 5 hours again, obtained sample;
(2) with the sample of step (1) gained in 100 ℃ of baking ovens dry 4 hours, go to again Muffle furnace in nitrogen environment in 400 ℃ of roastings 1 hour, placing 400 ℃, hydrogen flow rate then is the reduction tube reductase 12 hour of 40ml/min, promptly get improved copper ethylene absorbent, wherein the Cu percentage by weight is 2%, and the active carbon percentage by weight is 98%.
This absorbent is seen Fig. 2 to the adsorption penetration ability of ethene, and test method is with embodiment 1.
(1) adopts equi-volume impregnating, with 0.4008gCuCl
22H
2O is dissolved in the 7.5ml deionized water and is mixed with maceration extract, and the active carbon with the 5g activation flooded in maceration extract 5 hours again, obtained sample;
(2) with the sample of step (1) gained in 100 ℃ of baking ovens dry 4 hours, go to again Muffle furnace in nitrogen environment in 400 ℃ of roastings 1 hour, placing 400 ℃, hydrogen flow rate then is the reduction tube reductase 12 hour of 40ml/min, promptly get improved copper ethylene absorbent, wherein the Cu percentage by weight is 3%, and the active carbon percentage by weight is 97%.
This absorbent is seen Fig. 3 to the adsorption penetration ability of ethene, and test method is with embodiment 1.
Embodiment 4
(1) adopts equi-volume impregnating, with 0.2671gCuCl
22H
2O is dissolved in the 10ml deionized water and is mixed with maceration extract, and the aluminium oxide with the 5g activation flooded in maceration extract 6 hours again, obtained sample;
(2) with the sample of step (1) gained in 80 ℃ of baking ovens dry 5 hours, go to Muffle furnace again in 300 ℃ of roastings 1 hour, placing 400 ℃, hydrogen flow rate then is reduction tube reductase 12 .5 hour of 60ml/min, promptly get improved copper ethylene absorbent, wherein the Cu percentage by weight is 2%, and alumina weight percentage is 98%.
This absorbent is seen Fig. 5 to the adsorption penetration ability of ethene, and test method is: under the room temperature normal pressure, be that gas flow rate is 64ml/min, detects the concentration of ethene in the tail gas in the air feeding improved copper ethylene absorbent of 300ppm with ethylene concentration.
Embodiment 5
(1) adopts equi-volume impregnating, with 0.2671gCuCl
22H
2O is dissolved in the 10ml deionized water and is mixed with maceration extract, the 5g activated zeolites is flooded in maceration extract 10 hours again, obtains sample;
(2) with the sample of step (1) gained in 110 ℃ of baking ovens dry 4 hours, go to Muffle furnace again in 400 ℃ of roastings 2 hours, placing 350 ℃, hydrogen flow rate then is the reduction tube reduction 3 hours of 30ml/min, promptly get improved copper ethylene absorbent, wherein the Cu percentage by weight is 2%, and the zeolite percentage by weight is 98%.
This absorbent is seen Fig. 6 to the adsorption penetration ability of ethene, and test method is with embodiment 4.
Embodiment 6
(1) adopts equi-volume impregnating, with 0.3781gCu (NO
3)
23H
2O is dissolved in the 10ml deionized water and is mixed with maceration extract, and HY (Si/Al=2.8) the type molecular sieve with the 5g activation flooded in maceration extract 10 hours again, obtained sample;
(2) with the sample of step (1) gained in 100 ℃ of baking ovens dry 3 hours, go to Muffle furnace again in 400 ℃ of roastings 1.5 hours, placing 400 ℃, hydrogen flow rate then is the reduction tube reductase 12 hour of 40ml/min, promptly get improved copper ethylene absorbent, wherein the Cu percentage by weight is 2%, and HY (Si/Al=2.8) type molecular sieve percentage by weight is 98%.
This absorbent is seen Fig. 7 to the adsorption penetration ability of ethene, and test method is with embodiment 4.
Embodiment 7
(1) adopts equi-volume impregnating, with 0.3782gCu (NO
3)
23H
2O is dissolved in the 10ml deionized water and is mixed with maceration extract, and the diatomite with the 5g activation flooded in maceration extract 10 hours again, obtained sample;
(2) with the sample of step (1) gained in 100 ℃ of baking ovens dry 3 hours, go to Muffle furnace again in 400 ℃ of roastings 1.5 hours, placing 400 ℃, hydrogen flow rate then is the reduction tube reductase 12 hour of 40ml/min, promptly get improved copper ethylene absorbent, wherein the Cu percentage by weight is 2%, and the diatomite percentage by weight is 98%.
This absorbent is seen Fig. 8 to the adsorption penetration ability of ethene, and test method is with embodiment 4.
Claims (4)
1. the application of improved copper ethylene absorbent in fruits and vegetables and flower freshness, it is characterized in that: the preparation method of described improved copper ethylene absorbent may further comprise the steps:
(1) adopt equi-volume impregnating, mantoquita is dissolved in is mixed with maceration extract in the deionized water, the carrier with activation flooded 5 hours in maceration extract at least then, obtained sample; Described mantoquita is Cu (NO
3)
2, CuCl
2In one or both;
(2) with the sample of step (1) gained in 80～110 ℃ of dryings 3～5 hours, again in 300～400 ℃ of roastings 1～2 hour, be reductase 12～3 hour in the hydrogen of 30～60ml/min in 300～400 ℃, flow velocity then, promptly get improved copper ethylene absorbent;
The weight percentage of metallic copper is 0.1%～6% in the described improved copper ethylene absorbent, and the weight percentage of carrier is 94%～99.9%;
Described carrier is a kind of in active carbon, molecular sieve, diatomite, the aluminium oxide.
2. application according to claim 1 is characterized in that: described carrier is an active carbon, and the roasting in the step (2) is carried out in nitrogen environment.
3. application according to claim 1, it is characterized in that: described carrier is an active carbon, activation method is: be that 30% aqueous solution of nitric acid refluxed 4 hours in 60 ℃ of water-baths with the active carbon mass percentage concentration, spend deionised water at last to neutral, promptly get the active carbon that activates after the drying.
4. application according to claim 1, it is characterized in that: described carrier is aluminium oxide, diatomite or molecular sieve, activation method is: with after aluminium oxide, diatomite or the molecular sieve drying in 200～500 ℃ of roastings 2～3 hours, pulverize the back and cross 20～60 mesh sieves, tail over and be granularity 20～60 purpose activated carriers.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566869B (en) * | 2013-11-20 | 2016-01-20 | 西南化工研究设计院有限公司 | A kind of cupric adsorbent of molecular sieve and preparation method thereof |
| CN104998606B (en) * | 2014-12-12 | 2018-01-12 | 北京恩泽福莱科技有限公司 | A kind of method of non basic nitrogen compound in removing hydrocarbon products |
| CN105494318B (en) * | 2015-07-21 | 2018-11-02 | 大连医科大学 | A kind of application of activated carbon supported Cu-Mn complex oxide material |
| CN105638868B (en) * | 2015-12-29 | 2019-11-29 | 浙江工业大学 | A kind of fresh-keeping coating material for fruit and vegetable and its preparation and application |
| CN107398249B (en) * | 2016-05-18 | 2020-05-12 | 中国石油化工股份有限公司 | Purifying agent for butadiene tail gas and preparation method thereof |
| CN108212201B (en) * | 2017-12-07 | 2021-12-21 | 中国科学院上海高等研究院 | Catalyst with copper nanoparticles loaded on molecular sieve, and preparation method and application thereof |
| CN114190430B (en) * | 2021-12-10 | 2024-02-27 | 中国热带农业科学院南亚热带作物研究所 | Fresh-keeping material capable of efficiently removing ethylene and preparation method thereof |
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| CN1136978A (en) * | 1996-03-25 | 1996-12-04 | 中国科学院成都有机化学研究所 | Selective ethene adsorbent and producing process thereof |
| CN101371979A (en) * | 2008-10-10 | 2009-02-25 | 天津大学 | Sorbent for absorbing carbon dioxide in trace amounts of ethylene and preparation method thereof |
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2009
- 2009-02-27 CN CN2009100962227A patent/CN101513604B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1136978A (en) * | 1996-03-25 | 1996-12-04 | 中国科学院成都有机化学研究所 | Selective ethene adsorbent and producing process thereof |
| CN101371979A (en) * | 2008-10-10 | 2009-02-25 | 天津大学 | Sorbent for absorbing carbon dioxide in trace amounts of ethylene and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 吉定豪 等.Cu/ZSM-5催化剂的表征及其环己醇脱氢性能.《石油化工》.2007,第36卷(第6期),570-574. * |
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