Patent Application
20100285190
The instant invention relates to a process for removing ethene from biological sources using metal ion exchanged titanium zeolites. Further aspects of the invention are polymer compositions containing these zeolites, their use as efficient ethene removing additives and the modified titanium zeolites self.
Eliminating ethene gas, which is generated during storage of biological products, such as fruits, flowers and the like, is an effective way to prolong the post-harvest life of fresh vegetables, fruits and cut flowers. The high concentration of ethene gas accelerates the aging of fresh products.
A number of solutions already exist on the market, based on different technologies. For example ethene can be removed by chemical reaction and this is what happens with potassium permanganate based systems. It can also be removed by adsorption, which is the principle function of zeolites, oya stones and other inorganic additives, most often incorporated into plastic packaging films. This is for example described in EP 1 134 022. A further possibility is by means of catalytic filters which purify the air. All these solutions have drawbacks coming from the low activity of inorganic additives in plastic films or from the toxicity of permanganate based sachets with consequent difficult disposal.
The present invention overcomes the above drawbacks by providing means for adsorbing and decomposing ethene. The combined use of both principles leads to an excellent result for removing the plant hormone ethene with the consequence of an increased fresh post-harvest life and therefore improved quality.
One aspect of the invention is a process for removing ethene from a gas atmosphere, comprising
bringing into contact a porous titanium zeolite with partly replaced alkaline metal ions by Cu(II) or Ag(I) ions of formula (I), (II) or (III)
Mey(NaK)2-yTiSi5O13H2O (I),
(1+x/2)(1±0.25Me2/nO):TiO2:xAl2O3:ySiO2:zH2O (II)
MeyNa9-ySi12Ti5O3812H2O (III)
wherein
Me is Ag(I) or Cu(II), n in the case of Ag(I) is 1 and in the case of Cu(II) is 2;
x is a number from 0.5 to 5
y is a number from 0.5 to 5 and
z is a number from 0.5 to 30;
with a gas atmosphere containing at least partly ethene and letting the porous titanium zeolite adsorb the ethene.
In general compounds from the series of the zeolites (alkali metal and/or alkaline earth metal aluminosilicates) can be described by the general formula (IV)
Mx/n[(AlO2)x(SiO2)y].wH2O (IV)
in which n is the charge of the cation M;
M is an element from the first or second main group, such as Li, Na, K, Mg, Ca, Sr or Ba, or Zn,
y:x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and
w is a number from 0 to 300, preferably from 0.5 to 30.
Structures can be found, for example, in the “Atlas of Zeolite” by W. M. Meier and D. H. Olson, Butterworth-Heinemann, 3rd ed. 1992.
Examples of zeolites are sodium alumosilicates of the formulae
Na12Al12Si12O48. 27H2O [zeolite A], Na6Al6Si6O24.2 NaX.7.5H2O, X═OH, halogen, ClO4 [sodalite]; Na6Al6Si30O72.24H2O; Na8Al8Si40O96.24H2O; Na16Al16Si24O80.16H2O; Na16Al16Si32O96.16H2O; Na96Al96Si136O384.250H2O [zeolite Y], Na96Al96Si106O384.264H2O [zeolite X];
or the zeolites which can be prepared by partial or complete exchange of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as
(Na,K)10Al10Si22O64.20H2O; Ca4.5Na3[(AlO2)12(SiO2)12].30H2O; K9Na3[(AlO2)12 (SiO2)12].27H2O.
The zeolites used as starting materials before the Cu(II) or Ag(I) ions are incorporated have additionally titanium incorporated. Examples are: (NaK)2TiSi9O13H2O and Na9Si12Ti5O38 12H2O. Suitable starting zeolites are commercially available and for example sold under the trade name ETS-10, ETAS-10 and ETS-4 by Engelhard Inc.
Crystalline titano-silicates have a porous Zeolite-type framework. With the porous structure they can absorb ethene. The titanium of the framework can act as photocatalyst in the presence of light thus destroying the adsorbed ethene if irradiated. They have high exchange capacity which allows functionalization with an ethene complexing metal ion, such as silver and copper to enhance the activity.
The present invention uses a zeolite containing in the framework titanium, silicon and optionally aluminum, manufactured for example by Engelhard Inc., where the exchangeable cations have been partly exchanged with copper (II) and/or silver (I) ions in order to obtain a selective ethene scavenger.
The commercial zeolites are dispersed in water and a soluble Ag(I) or Cu(II) salt is added. Typically silver nitrate and copper (II) acetate may be used. The solution is stirred for 1 to 40 hours at a temperature between 20° C. and 95° C. After filtering and drying the ion exchanged product is obtained as a powder.
In a preferred process the ethene containing porous titanium zeolite of formula (I), (II) or (III) is exposed to actinic radiation.
Actinic radiation means natural or artificial light in the range from 300 to 700 nm, preferably from 300 to 500 nm.
As plants are still alive after being harvested, various physiological effects such as respiration effect, transpiration effect, mold growth and putrefaction under the action of microorganisms, etc. may take place and accelerate the loss of freshness of the plants. In addition, plants evolve ethene, a kind of plant hormone, as a metabolite. Ethene has many physiological effects, among which there are a respiratory promoting effect and maturity promoting effect, and, therefore, largely relates to maturity and also loss of freshness of the plants. The loss of freshness has been a problem especially in the storage or the distribution of vegetables, fruits and flowers. A post harvest preservation to maintain freshness of vegetables, fruits and flowers is therefore highly desirable.
The instant process is particularly useful when the ethene is generated during the storage of fruits, flowers or vegetables.
For example, the porous titanium zeolite of formula (I), (II) or (III) may be used in polymer products, such as plastic films, sheets, bags, bottles, styrofoam cups, plates, utensils, blister packages, boxes, package wrappings, plastic fibers, tapes, twine agricultural films, disposable diapers, disposable garments, shop bags, refuse sacks, cardboard boxes, filtering devices (for refrigerators) and the like. The articles may be manufactured by any process available to those of ordinary skill in the art including, but not limited to, extrusion, extrusion blowing, film casting, film blowing, calendering, injection molding, blow molding, compression molding, thermoforming, spinning, blow extrusion and rotational casting.
In particular, this is of interest in the area of packaging articles, such as films, boxes, filters, labels, bags and sachets. The rate of the gas decomposition can be adjusted by simply changing the concentration of the porous titanium zeolite of formula (I), (II) or (III) and light exposure.
Particularly suitable is the incorporation in sachets made from cellulosic materials.
For example the porous titanium zeolite of formula (I), (II) or (III) is incorporated in a natural or synthetic polymer material.
Suitable natural or synthetic polymers are mentioned below.
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethene (which optionally can be crosslinked), for example high density polyethene (HDPE), high density and high molecular weight polyethene (HDPE-HMW), high density and ultrahigh molecular weight polyethene (HDPE-UHMW), medium density polyethene (MDPE), low density polyethene (LDPE), linear low density polyethene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethene and polypropylene, can be prepared by different, and especially by the following, methods:
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethene/propylene copolymers, linear low density polyethene (LLDPE) and mixtures thereof with low density polyethene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethene/but-1-ene copolymers, ethene/hexene copolymers, ethene/methylpentene copolymers, ethene/heptene copolymers, ethene/octene copolymers, ethene/vinylcyclohexane copolymers, ethene/cycloolefin copolymers (e.g. ethene/norbornene like COC), ethene/1-olefins copolymers, where the 1-olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethene/vinylcyclohexene copolymers, ethene/alkyl acrylate copolymers, ethene/alkyl methacrylate copolymers, ethene/vinyl acetate copolymers or ethene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethene-propylene copolymers, LDPE/ethene-vinyl acetate copolymers (EVA), LDPE/ethene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
Homopolymers and copolymers from 1.)-4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).
6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, α-methylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic, or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethene/butylene/styrene or styrene/ethene/propylene/styrene.
6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).
Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated polyethene, copolymers of ethene and chlorinated ethene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from α,β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethene and those polyoxymethenes which contain ethene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethene glycol, polypropylene glycol or polytetramethene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polyketones.
21. Polysulfones, polyether sulfones and polyether ketones.
22. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
23. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
For instance the natural or synthetic polymer material is celluose, a polyolefin, polystyrene or polyester.
Preferred is a process wherein the natural or synthetic polymer material is a packaging material for fruits, flowers or vegetables.
Typically the porous titanium zeolite of formula (I), (II) or (III) is present in an amount of 0.001 to 10% based on the weight of the natural or synthetic polymer material.
Another aspect of the invention is a composition comprising a porous titanium zeolite with partly replaced alkaline metal ions by Cu(II) or Ag(I) ions of formula (I), (II) or (III)
Mey(NaK)2-yTiSi5O13xH2O (I),
(1+x/2)(1±0.25Me2/nO):TiO2:xAl2O3:ySiO2:zH2O (II)
MeyNa9-ySi12Ti5O3812H2O (III)
wherein
Me is Ag(I) or Cu(II), n in the case of Ag(I) is 1 and in the case of Cu(II) is 2;
x is a number from 0.5 to 5
y is a number from 0.5 to 5 and
z is a number 0.5 to 30;
and a natural or synthetic polymer.
A further aspect is the use of a porous titanium zeolite with partly replaced alkaline metal ions by Cu(II) or Ag(I) ions of formula (I), (II) or (III)
Mey(NaK)2-yTiSi5O13xH2O (I),
(1+x/2)(1±0.25Me2/nO):TiO2:xAl2O3:ySiO2:zH2O (II)
MeyNa9-ySi12Ti5O3812H2O (III)
wherein
Me is Ag(I) or Cu(II), n in the case of Ag(I) is 1 and in the case of Cu(II) is 2;
x is a number from 0.5 to 5
y is a number from 0.5 to 5 and
z is a number 0.5 to 30;
for the removal of ethene in a gas atmosphere.
Yet another aspect is a porous titanium zeolite with partly replaced alkaline metal ions by Cu(II) or Ag(I) ions of formula (I), (II) or (III)
Mey(NaK)2-yTiSi5O13xH2O (I),
(1+x/2)(1±0.25Me2/nO):TiO2:xAl2O3:ySiO2:zH2O (II)
MeyNa9-ySi12Ti5O3812H2O (III)
wherein
Me is Ag(I) or Cu(II), n in the case of Ag(I) is 1 and in the case of Cu(II) is 2;
x is a number from 0.5 to 5
y is a number from 0.5 to 5 and
z is a number 0.5 to 30.
The above described porous titanium zeolite with partly replaced alkaline metal ions by Cu(II) or Ag(I) ions is a highly effective photocatalyst, which can be also used for pollutant removal, air cleansing, water purification, treatment of wet waste, odor removal, antimicrobial (e.g. roofing and tiles), anti-septic, anti-dust and anti-fog purposes.
The term wet waste means waste waters, wet solid waste, sludges and polluted air.
The term waste waters, means polluting waste, more or less thick liquids or fluids, such as for example: waste waters deriving from industrial processes and/or productions; sewages deriving from agricultural activities and zootechnical activities, such as drainage waters from breedings, abattoirs, fishing industries; waste waters from civil settlements, such as houses, shops, offices and hospitals; rain waters or washing waters from squares, roads, parking areas, car washes; motorway drainage waters and from refuelling; drainage waters from recycling plants and waste selection, leachates from disposal sites and from garbage cans.
By the term solid wet waste, it is understood to mean waste of a different nature such as, for example, domestic and hospital waste, urban solid waste, putrescible organic waste, green waste.
By the term sludges, it is understood to mean solid or semisolid waste deriving from urban, industrial, agricultural zootechnical waste, or decantation sludges from purification processes, for example of a biological type.
By the term polluted air, it is understood to mean air polluted by toxic or malodorous, gaseous or volatile matters, deriving from human activities, from production processes, from biological purification or from processing plants of solid waste. For example, there may be mentioned the ammonia liberated from animal sewages in the breedings, the organic solvents employed in the paints and glues industry and so on.
By the term polluting agents, it is understood to mean each type of toxic or malodorous matter which is harmful for the human being and/or the environment, such as, by way of non limiting example: volatile or not volatile organic substances, of a different nature, origin and composition, for example halogenated residues, drugs, oils, greases, surfactants, detergents, fertilizers, solvents; inorganic substances, such as metals, in particular heavy metals, salts; nitrogenous, sulfurous and phosphoric residues. In particular, among the polluting agents, those harmful substances which are not degradable with the known biological purification systems are preferred. One of the aims of the treatment of wet waste is the removal from the same of the polluting agents, in order to eliminate or, at least considerably decrease the possibility of harmful effects on human being and the rest of the ecosystem. General classes of concern include: solvents, volatile organics, chlorinated volatile organics, dioxins, dibenzofurans, pesticides, PCB's, chlorophenols, asbestos, heavy metals, and arsenic compounds. Some specific compounds of interest are 4-chlorophenol, pentachlorophenol, trichloroethylene (TCE), perchloroethylene, CCl4, HCCl3, CH2Cl2, ethylene dibromide, vinyl chloride, ethylene dichloride, methyl chloroform, p-chlorobenzene, and hexachlorocyclopentadiene. The occurrence of TCE, PCE, CFC-113 (i.e. Freon-113) and other grease-cutting agents in soils and groundwaters is widespread.
The following examples illustrate the invention.
Titanium zeolites were purchased from Engelhard Inc. Commercial name: ETS-10.
ETS-10 general formula: (NaK)2TiSi5O13xH2O
Ag-TS-10: general formula Agy(NaK)2-yTiSi5O13xH2O where y˜1.4 and x˜2.3
To a 100 ml round bottom flask containing the titanium zeolite ETS-10 (3 g), a 1M solution of silver nitrate (20 ml) is added under nitrogen atmosphere. The mixture is magnetically stirred at 85° C. under nitrogen for 5 hours. After the reaction mixture is cooled down to room temperature the solid is filtered in a Buchner funnel and washed with deionized water until the washing waters are free from silver ions (chloride test).
The resulting white solid is dried at 110° C. for 16 hours. 4.5 g of a brownish powder are obtained. Silver content (determined via ICP analysis): 26%
ETS-10 general formula: (NaK)2TiSi5O13xH2O
Cu-TS-10: general formula Cuy(NaK)2-2yTiSi5O13xH2O where y˜0.7 and x˜1.9
To a 500 ml flask containing the titanium zeolite ETS-10 (4 g), a 0.01M solution of copper(II) acetate monohydrate (260 ml) is added. The mixture is magnetically stirred at room temperature for 24 hours. The solid is then filtered in a Buchner funnel and the obtained wet cake is again ion exchanged in a new copper acetate monohydrate 0.01M solution (260 ml). After three ion-exchange treatments the zeolite is washed with deionized water (˜250 ml), dried under vacuum at 110° C. for 16 hours and calcined at 500° C. for 5 hours. 4 g of a light green powder are obtained. Copper content (ICP): 11%
A given amount of exchanged zeolite (80 mg) is transferred in a Schlenk tube (100 ml) and a certain amount of air/ethene gas mixture is injected in the tube. The composition of the gas mixture contained in the Schlenk tube is monitored over time as reported in Table 1 below.
To initiate photooxidation, the sample tubes are exposed either to ambient light or in a Weatherometer (model ATLAS Ci65A) equipped with a 6500W Xenon lamp (continuous light cycle, black panel temperature=63° C.) for several hours. The results are given in Table 1.
The silver containing sample decomposes the ethene gas by complexing and oxidation already without light exposure almost completely. The copper containing sample decomposes the ethene gas to certain extent by complexing and oxidation in the dark, upon exposure to light a further decrease in ethen concentration takes place. The total ethen decomposition of samples 1 and 2 is significantly higher than that of the comparative untreated sample.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2007/055689 | 6/11/2007 | WO | 00 | 3/25/2010 |
