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    • 专利摘要:
    Elimination of ultra-low concentrations of ethylene in air currents at low temperature. The present invention describes a process for removing traces of ethylene in low temperature air streams comprising: - a first step where the air stream is introduced into a first reactor; - a second step in which the effluent from the first step is fed into another reactor where there is a metal oxide; - recovery of the exit gas stream; With applications in preservation of fruits, vegetables or combinations of them during storage or transport. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2653703A1
    申请号:ES201630908
    申请日:2016-07-04
    公开日:2018-02-08
    发明作者:Avelino Corma Canós；Larisha Yanira CISNEROS REYES；Fei Gao
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

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    ELIMINATION OF ULTRA-LOW ETHYLENE CONCENTRATIONS IN LOW TEMPERATURE AIR CURRENTS
    DESCRIPTION
    Field of the Invention
    This invention relates to a process for the removal of traces of ethylene, as well as other compounds such as carbon dioxide and mixtures in air currents at low temperatures, using, among others, materials based on cobalt oxides, with preservation application of fruits, vegetables and / or ornamental during storage or transport.
    Background
    Ripening is a metabolic process of cut fruits, vegetables and flowers that causes most fruits to become sweeter, less green and softer and edible. It is well known that this metabolic process can be minimized by reducing oxygen and decreasing temperature. In climacteric fruits and vegetables, the metabolism is accelerated by the presence of low concentrations of ethylene. This ethylene can be emitted directly by fresh stored products. The continuous and uncontrolled activity of said biochemical process, caused by the production of ethylene after ripening, leads to the decomposition of fruits and vegetables, and makes them unfit for consumption. For example, concentrations of 1 ppm can destroy a whole container of products in one day. Due to this, the prevention of the deterioration or damage of fruits and vegetables by increasing their useful life is of paramount importance for their consumption in longer times or to transport them to distant places where they are not normally available. Therefore, the removal of traces of ethylene (preferably below 1 ppm) from air currents at low temperature (approximately 0 ~ 4 ° C) is essential. Given the above, there are a number of technological methods focused on the elimination of ethylene that are commercially available, which are based on the adsorption / oxidation / blocking of ethylene. In the blocking method, binding agents are required, which implies an additional packaging cost as well as the need for further processing of said compounds. On the other hand, adsorption processes are always an efficient way to eliminate ethylene. However, the adsorbents
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    they are regenerated by heating in an inert atmosphere, while the adsorbed ethylene is released during the regeneration process. The ethylene oxidation is a thermodynamically favored process, since it is thermally stable and oxidation is generally carried out in the presence of catalysts. For example, Hao et al. in "JAm Chem. Soc., 132, page 2608-2613 of 2010, Enivrion. Sci. Technol., 42, p8947-8951, and Catal. Commun., 12, 2011, p1265-1268" describes the development of catalysts for Gold supported on Co3O4 for the elimination of ethylene at low temperature. On the other hand, Jiang et al. in "Angew. Chem. Int. Ed., 52, 2013, p6265-6268" uses a Pt catalyst supported on mesoporous silica that gives complete conversions of ethylene at low temperature. However, for these low temperature oxidation processes the use of precious metals (Au, Pd) is required and the duration of these materials as well as their high cost remains an important problem.
    Additionally, the effective removal of CO2 and water vapor in ethylene streams in the same bed of adsorbent / catalyst is not easy to achieve, since water has a higher affinity for adsorbents than for CO2. To achieve this goal, a common practice is to use a 13X type zeolite to remove CO2 since the 13X zeolite is particularly known for its effectiveness in stopping small amounts of ethylene, CO2 and possibly water as mentioned in Breck “ Zeolite molecular sieves ”, Krieger Publishing Company, 1984, p.612. However, as indicated in Dr. J. Reyhing “Removal hydrocarbons from the process air of air separation plants using molecular sieve adsorbers”, Linde Reports on Science and Technology, 36/1983, the use of a pre-purification unit air to remove carbon dioxide with a zeolite, typically 13X or 5A zeolite, only partially removes ethylene, propane and nitrogen protoxide, which is insufficient when the removal of traces of ethylene is required in carbon dioxide rich streams.
    On the other hand, there are documents that describe the use of zeolitic adsorbents to remove ethylene or nitrogen protoxide, for example, the use of activated carbon and a CaA zeolite for the purification of the atmosphere in fruit and vegetable preservation chambers; However, this does not completely solve the problem of eliminating ethylene from air currents.
    Thus, although certain documents provide more or less effective solutions that allow eliminating some of the impurities that can be found in atmospheric air, it seems that the problem of eliminating ethylene in air currents that
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    They also contain CO2 and their mixtures with water, it has not been satisfactorily resolved so far. In the present invention, a less expensive and lower energy consumption way for the elimination of ethylene, CO2 and their mixtures in air is described.
    Description of the invention
    The present invention describes a process for the removal of traces of ethylene in air streams that may comprise at least:
    - a first step where the air stream is introduced into a reactor comprising at least one bed containing a material preferably selected from a zeolite preferably selected from zeolite A, X, Y, clinoptilolite and combinations thereof; amorphous silica, magnesium sulfate, sodium hydroxide, potassium hydroxide, potassium sulfate, calcium sulfate, potassium carbonate and combinations thereof;
    - a second step in which the effluent from the first step is fed into another reactor comprising at least one catalyst comprising at least one pure metal oxide, a metal oxide doped with transition metals or combinations thereof;
    - Recovery of the outlet gas stream;
    with applications in preservation of fruits, vegetables or combinations thereof during storage or transport
    According to a particular embodiment, the metal oxide of the second step may be doped with at least one transition metal selected from Ni, Co, Mo, Cu, Mn and combinations thereof, preferably being cobalt oxide that may be present in a percentage between 0.01 to 100% by weight.
    Metal oxides are easily regenerated with a stream of nitrogen or fresh air at a higher temperature.
    According to another particular embodiment, the cobalt oxide may further comprise a transition metal selected from Ni, Mo, Cu, Mn and combinations thereof where the cobalt is preferably in a percentage by weight with respect to the equal or higher metal at 60%
    According to a preferred embodiment, said transition metal is Ni.
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    According to another preferred embodiment, said transition metal is Mo.
    According to another preferred embodiment, said transition metal is Cu.
    According to another preferred embodiment, said transition metal is Mn.
    In the process described in the present invention, the air stream may be formed by at least ethylene, nitrogen, oxygen and combinations thereof, ethylene may be preferably present in amounts between 0.01-100 ppm. In addition, said stream may also comprise another compound selected from water, carbon dioxide and combinations thereof, water being present in a volume percentage preferably between 0.3 to 3% and carbon dioxide in a volume percentage. preferably between 0.01-3%.
    The process of the present invention is also characterized in that it is carried out at low temperatures, preferably between -5 ° and 25 ° C and more preferably between 0 and 4oC, as well as at a preferred pressure between 0.5 to 5 bar and more preferably it is carried out at atmospheric pressure.
    The metal oxides used in the second step of the present invention can be prepared through different means known in the state of the art, and preferably by a precipitation method, preferably by the ethylene glycol precipitation method.
    Thus, according to a preferred embodiment, the metal oxide of the second step can be prepared by a process comprising at least the following steps:
    - mixing at least one inorganic metal salt of sodium carbonate preferably selected from acetate, nitrate, carboxylate and combinations thereof and ethylene glycol, until a precipitate is obtained;
    - subsequently the precipitate of the previous step is calcined in air flow.
    According to a particular embodiment, the inorganic metal salt is cobalt acetate tetrahydrate and is mixed with ethylene glycol with sodium carbonate solution. The solid obtained was filtered, washed, dried and then calcined in air. The resulting cobalt oxide called "CoOx" can be used for the removal of ethylene from gaseous mixtures.
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    When we have the presence of more than one type of metal oxide, the method of production is the same using the appropriate proportions of the corresponding metal salts in the precipitation process. In this case, the materials obtained comprise co-precipitated cobalt oxide together with metals such as, for example, Ni, Mo, Cu, Mn and combinations thereof, where the metal or metals other than Co are present in a preferably equal amount or less than 40% by weight of the metal. The removal of ethylene is carried out properly by passing the gaseous mixture containing 0.01 to 100 ppm of C2H4 / 5-30% O2 with balanced N2 (the percentage corresponds to volume) through the metal oxides at temperatures of between -5 ° D-25 ° C and pressures between 0.5-5 bar. The gas flow rate with respect to the amount of metal oxide is between 200l / minute and 2000l / minute per kilogram of solid.
    According to the process of the present invention, the material regeneration cycle can be carried out by treating the metal oxides with fresh air at a temperature between 20 and 300 ° C.
    As described in a particular embodiment of the present invention, the first step is carried out in a reactor comprising at least one bed that may contain amorphous silica, magnesium sulfate, sodium hydroxide, potassium hydroxide, sodium sulfate. potassium, calcium sulfate, potassium carbonate, or zeolite, such as: zeolite A, X, Y, clinoptilolite, and which can be placed before the second step system, which contains at least one metal oxide. In other words, the gas flow will first pass through the material of the first reactor and its effluent will be fed to the system containing it or the transition metals.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention.
    Brief description of the figures
    Figure 1: Elimination of Ethylene at 0 ° C with CoOx
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    Figure 2: Removal of Ethylene with CoNiOx at 0 ° C Figure 3: Removal of Ethylene with CoMoOx at 0 ° C Figure 4: Removal of Ethylene and CO2 at 0 ° C with CoMoOx
    The present invention is illustrated by the following examples that are not intended to be limiting thereof.
    EXAMPLES
    Example 1. Preparation of CoOx
    5.0 g of tetrahydrated cobalt acetate were dissolved in 60 ml of ethylene glycol and the mixture was gradually heated to 160 ° C. Then 200 ml of 0.2 M aqueous sodium carbonate solution was added and the suspension was aged for 1 h with vigorous stirring and continuous nitrogen flow. After filtration, it was washed with water and the solid obtained was dried under vacuum and 50 ° C overnight; subsequently it was calcined at 450 ° C for 4 h in air.
    Example 2. Preparation of NiCoOx
    5.0 g of tetrahydrated cobalt acetate together with the required amount of nickel acetate were dissolved in 60 ml of ethylene glycol and the mixture was gradually heated to 160 ° C. Then 160 ml of 0.2 M aqueous sodium carbonate solution was added and the suspension was aged for 1 h with vigorous stirring and continuous nitrogen flow. After filtration, it was washed with water and the solid obtained was dried under vacuum and 50 ° C overnight; subsequently and calcined at 450 ° C for 4 h in air. The metal oxide contained 20% by weight nickel oxide.
    Example 3. Preparation of MoCoOx
    5.0 g of cobalt acetate tetrahydrate together with the required amount of ammonium molybdate were dissolved in 100 ml of ethylene glycol and the mixture was gradually heated to 160 ° C. Then 160 ml of 0.2 M aqueous sodium carbonate solution was added and the suspension was further aged for 1 h with vigorous stirring and continuous nitrogen flow. After filtration, it was washed with water, and the solid obtained was dried under vacuum and 50 ° C overnight and then calcined at 450 ° C for 4 h in air. The metal oxide contained 20% by weight molybdenum oxide.
    Example 4. Elimination of ethylene at low temperature with CoOx
    The elimination of ethylene was measured at 0 ° C and 1 atmosphere through a gas mixture containing 10 ppm C2H4 / 10% O2 with equilibrium N2 (volume percentage) with a flow of 20 ml / min that was passed on a continuous fixed bed reactor containing 150 mg CoOx in the form of pellets, the composition of the gas stream at the outlet was measured and the results shown in Figure 1 indicate more than 96% removal of ethylene during 10 continuous hours without loss of catalytic activity.
    10 Example 5. Elimination of ethylene at low temperature with CoNiOx
    The removal of ethylene was measured at 0 ° C, and 1 atm. absolute by passing the gaseous mixture containing 10 ppm C2H4 / 10% O2 with equilibrium N2 (volume percentage) with a flow rate of 20 ml / min which was passed over a continuous fixed bed reactor containing 150 mg CoNiOx in the form of pellets, the composition of the gas stream at the outlet was measured and the results indicated in Figure 2 indicate the removal of ethylene by more than 95% for 13 hours without losing the catalytic activity.
    Example 6. Elimination of ethylene at low temperature with CoMoOx
    The removal of ethylene was measured at 0 ° C, and 1 atm. Absolute by passing the gas mixture containing 10 ppm C2H4 / 10% O2 with equilibrium N2 (volume percentage) with a flow rate of 20 ml / min which was passed over a continuous fixed bed reactor containing 150 mg CoMoOx in the form of pellets, the composition of the gas stream at the outlet was measured and the results indicated in Figure 3 indicate the removal of ethylene by more than 96% for 13 hours without loss of catalytic activity.
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    Example 7
    The removal of ethylene was measured at 0 ° C, and 1 atm. Absolute by passing the gaseous mixture containing 10 ppm C2H4 / 10% O2 / 0.6% H2O with N2 balance (volume percentage) with a flow rate of 20 ml / min over the sample bed, which was made per 150 mg of pellets with a 20-40 mesh of CoOx, CoMoOx and CoNiOx. The results are presented in Table 1, and show how water resistance can be improved by CoOx doping with nickel or molybdenum ions.
    Table 1. Influence of water on CoOx and doped metal oxides
     Catalyst  Time (h)
     CoOx  0.5
     CoMoOx  one
     CoNiOx  3
    Example 8
    The removal of ethylene was measured at 0 ° C, and 1 atm. absolute by passing two gaseous mixtures one with a flow rate of 20 ml / min containing 10 ppm C2H4 / 10% O2 5 balance N2 (volume percentage) and another 5 ml / min containing 0.3% CO2 with balance N2 (percentage by volume) on the sample bed, which was made for 150 mg in the form of CoOx pellets. According to Figure 4, the catalytic activity of CoOx is not affected by the presence of CO2 during 9 hours of reaction.
    权利要求:
    Claims (21)
    [1]
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    1. Procedure for eliminating traces of ethylene in air currents characterized in that it comprises at least:
    - a first step where the air stream is introduced into a reactor comprising at least one bed containing a material selected from a zeolite, amorphous silica, magnesium sulfate, sodium hydroxide, potassium hydroxide, potassium sulfate, calcium sulfate, potassium carbonate and combinations thereof;
    - a second step in which the effluent from the first step is fed into another reactor comprising at least one catalyst comprising at least one pure metal oxide, a metal oxide doped with transition metals or combinations thereof.
    - Recovery of the outlet gas stream.
    [2]
    2. Method for removing traces of ethylene according to claim 1, characterized in that the zeolite of the first step is selected from A, X, Y, clinoptilolite and combinations thereof.
    [3]
    3. - Procedure for removing traces of ethylene according to claim 1,
    characterized in that the metal oxide of the second step is doped with at least one transition metal selected from Ni, Co, Mo, Cu, Mn and combinations thereof.
    [4]
    4. - Procedure for removing traces of ethylene according to claim 3,
    characterized in that the metal oxide of the second step is a cobalt oxide.
    [5]
    5. - Procedure for removing traces of ethylene according to claim 4,
    characterized in that cobalt oxide is present in a percentage between 0.01 to 100% w / w by weight.
    [6]
    6. Procedure for removing traces of ethylene according to claims 4 and 5, characterized in that the cobalt oxide further comprises a transition metal selected from Ni, Mo, Cu, Mn and combinations thereof and where the cobalt is located in a percentage by weight with respect to metal equal to or greater than 60%.
    [7]
    7. Ethylene trace removal method according to claim 6,
    characterized in that the transition metal is nickel.
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    [8]
    8. Ethylene trace removal method according to claim 6,
    characterized in that the transition metal is molybdenum.
    [9]
    9. Ethylene trace removal method according to claim 6,
    characterized in that the transition metal is copper.
    [10]
    10. Ethylene trace removal method according to claim 6,
    characterized in that the transition metal is manganese.
    [11]
    11. Procedure for removing traces of ethylene according to any of claims 1 to 10, characterized in that the air flow is formed by at least ethylene, nitrogen, oxygen and combinations thereof.
    [12]
    12. Ethylene trace removal method according to claim 11, characterized in that the air stream further comprises another compound
    selected from water, carbon dioxide and combinations thereof.
    [13]
    13. Ethylene trace removal procedure according to any of the
    claims 1 to 12, characterized in that ethylene is present in amounts between 0.01-100 ppm.
    [14]
    14. Method for removing traces of ethylene according to claim 12, characterized in that the water is present in a percentage by volume between 0.3 to 3% and carbon dioxide in a percentage by volume between 0.01-3% .
    [15]
    15. Ethylene trace removal procedure according to any of the
    claims 1 to 14, characterized in that it is carried out at a temperature between -5 °
    and 25 ° C.
    [16]
    16. Ethylene trace removal method according to claim 15, characterized in that it is carried out at a temperature between 0 and 4 oC.
    [17]
    17. Ethylene trace removal procedure according to any of the
    claims 1 to 16, characterized in that it is carried out at a pressure between 0.5 to 5 bar.
    [18]
    18. Ethylene trace removal method according to claim 17, characterized in that it is carried out at atmospheric pressure.
    [19]
    19. Ethylene trace removal method according to any one of claims 1 to 18, characterized in that the metal oxide of the second step is
    Prepare by means of a process that includes at least the following steps:
    - mixing at least one inorganic metal salt of sodium carbonate and ethylene glycol, until a precipitate is obtained;
    - subsequently the precipitate of the previous step is calcined in air flow before coming into contact with the air stream.
    [20]
    20. Ethylene trace removal method according to claim 19, characterized in that the inorganic metal salt is selected from acetate, nitrate, carboxylate and combinations thereof.
    fifteen
    [21]
    21. Procedure for removing traces of ethylene according to any one of claims 1 to 20, with applications in preservation of fruits, vegetables or combinations thereof during storage or transport.
    DRAWINGS
    image 1
    Figure 1
    image2
    Figure 2
    ^^ CoOxj
    ------- 1 ------- 1 --------- 1 ------- 1 ---------- 1 ----- - ■ --------- 1
    4 6 8 10
    Time (h)
    ■ FG-26 (CoNiOx) |
    -i 1 --------- 1 1 1 ------- 1 1 1 1—
    4 6 8 10 12
    Time (h)
    (OR
    C
    -5
    £ D
    = 1
    m
    3
    Final concentration of C2H4 (ppm)
    or
    OR-'
    or
    or
    ro
    or
    or
    co
    or
    or
    or
    or
    ai
    or
    or
    ro
    _one_
    _i_
    G)
    _
    00
    _
    or
    image3
    Figure 3
    Final concentration of C2H4 (ppm)
    O N) -fck <J> 00 O
    image4
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    同族专利:
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    ES2653703B1|2019-01-15|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE19855722A1|1998-12-03|2000-06-08|Nils Thomsen|Device for the adsorption of ethylene in low concentrations|
    EP1106233A1|1999-11-30|2001-06-13|Degussa AG|Process for the adsorption of ethylene|
    KR100490665B1|2000-11-06|2005-05-19|퓨리테크|Manufacturing method of oxidation catalysts for elimination of the ethylene gas|
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