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    • 专利摘要:
    Selective catalytic hydrogenation of acetylene in the presence of excess ethylene. The present invention describes a process for the purification of ethylene streams of industrial interest which may comprise, at least, the following steps: - A first stage in which the stream of ethylene with acetylene and hydrogen are brought into contact with the catalyst containing iron oxide nanoparticles. - A second stage of heating the obtained mixture. - A third stage of product recovery. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2680194A1
    申请号:ES201730053
    申请日:2017-01-18
    公开日:2018-09-04
    发明作者:Avelino Corma Canós；Antonio LEYVA PÉREZ；María TEJEDA SERRANO；José Ramón CABRERO ANTONINO
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    image 1
    SELECTIVE CATALYTIC HYDROGENATION OF ACETYLENE IN THE PRESENCE OF
    EXTENSION OF ETHYLENE DESCRIPTION
    Field of the Invention
    The present invention describes a process for the purification of ethylene streams of industrial interest by hydrogenation of acetylene with hydrogen in the presence of a solid catalyst containing iron oxide.
    Background
    Ethylene is the precursor of polyethylene (PE), the first plastic in terms of production volume (> 80 million tons per year) followed by polypropylene and polyvinyl chloride, and whose worldwide demand continues to increase (Allsopp, MW; Vianello, G. In the Ullmann Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA: 2000).
    Ethylene is produced industrially by the "stream cracking" method, which consists of thermal breakage of heavy hydrocarbons into lighter ones. In addition to ethylene, other light hydrocarbons such as ethane, propylene and acetylene (Kniel, L .; Winter, O .; Stork, K. Ethylene, keystone to the petrochemical industry are formed. New York: M. Dekker 1980) .
    For use in polymerization, crude ethylene streams have to undergo a series of pre-treatments to eliminate some by-products that damage radical polymerization. Specifically, one of the most important challenges in this field is the elimination of acetylene, since this compound slows the propagation of free radicals from polymerization, resulting in poor quality polyethylenes (Hiroshi, M .; Fumio, H .;, Miyuki H .; Tsutomu, K., Polymer Chemistry, 6, 1968, 2881-2888). The first technique that was developed industrially for the removal of acetylene in ethylene streams, consisting of the selective extraction of acetylene with solvents such as acetone, has given way to much more effective catalytic hydrogenation processes. For this, fixed bed reactors are used that make use of different formulations depending on the characteristics of the reactor used (Tiedtke, DB; Cheung, TTP; Leger, J .; Zisman, SA; Bergmeister, JJ; Deizer, GA, Chemicals Influencing the Activity of Palladium-Based Catalysts for the Selective Hydrogenation of Acetylene to Ethylene in Acetylene Converters, New York, NY: American Institute of Chemical Engineers, 2001, 586-607). The first catalytic hydrogenation processes used ethylene crudes without practically previous treatments, which were hydrogenated in reactors with supported nickel catalysts. These catalysts are active even in the presence of high amounts of sulphides but due to their toxicity and low selectivity they were replaced by palladium-based catalysts. However, palladium is easily poisoned with the oil components, so the chemical nature of the ethylene stream had to be modified. For this, the currents were previously enriched in C2 and the so-called "back-end" and "front-end" catalytic hydrogenation reactors were used. The difference between them is that in the "back-end" the enriched mixture is first hydrogenated with a stoichiometric amount of hydrogen and then passes through the demetanization reactor, while in the "front-end" the current is demetanized before entering to the hydrogenator, so that the feed contains more hydrogen (Adams, D .; Blankenship, S .; Geyer, I .; Takenaka, T., Front End & Back End Acetylene Converter Catalysts, 3rd Asian Ethylene Symposium on Catalyst and Processes, 2000).
    image2
    In both cases, palladium catalysts are used which, although less toxic and more selective than those of nickel, are expensive and partially poisoned over time. Therefore, a general method of selective hydrogenation of acetylene in excess of ethylene with cheaper and more robust catalysts is of clear interest. (Ingmar Bauer, Hans-Joachim Knölker, Chem. Rev., 2015, 115 (9), 3170–3387).
    The present invention addresses this unsolved problem, that is, obtaining a method catalyzed by cheap, non-toxic and robust metals, to selectively hydrogenate acetylene in excess of ethylene. This patent makes use of a solid catalyst containing iron oxide. The new technology mimics the mechanism of activation and transfer of hydrogen that nature uses, which is completely different from the mechanism of nickel and palladium. Nature, through a type of enzymes called hydrogenases, performs H2 heterolytic cleavage at Fe2 + centers combined with H + acceptor / donor centers (Wolfgang Lubitz, Hideaki Ogata, Olaf Rüdiger, Edward Reijerse, Chem. Rev. 2014, 114, 4081 −4148). Thus, the use of a biomimetic hydrogenation catalyst based on supported Fe2.3 + oxides, inserted or not on a simple solid capable of exerting the H + acceptor / donor auxiliary function, in combination with the high affinity of this catalyst for Acetylene with respect to ethylene, achieves a practical, cheap and non-toxic method of selective hydrogenation of acetylene for the purification of ethylene streams (Rajenahally V. Jagadeesh, Annette-Enrica Surkus, Henrik Junge, Marga-Martina Pohl, Jörg Radnik, Jabor Rabeah, Heming Huan, Volker Schünemann, Angelika Brückner, Matthias Beller, Science VOL 342, 2013).
    image3
    Description of the invention
    The present invention relates to a process for the purification of ethylene streams of industrial interest comprising at least the following steps:
    -  A first step in which a stream of ethylene comprising at least acetylene and hydrogen is contacted with a catalyst containing iron oxide.
    -  A second stage of heating the obtained mixture.
    -  A third stage of product recovery.
    In the first stage of the process, acetylene is selectively hydrogenated against ethylene preferably.
    According to a particular embodiment of the present invention, the amount of acetylene that the ethylene stream can contain is in amounts between 20 ppm and pure acetylene, preferably 100-10000 ppm.
    image4
    According to a particular embodiment of the present invention, the amount of hydrogen that can be used is 1 to 10 equivalents, preferably 1-3 equivalents with respect to ethylene.
    5 According to another particular embodiment, the ratio of acetylene to catalyst is between 10,000 and 10.
    As we have already mentioned, the process of the present invention requires an iron oxide catalyst, preferably nanoparticulate iron oxide. In addition, the iron oxide may be supported or intimately mixed (inserted) with compatible solids, defining compatible solid as that which supports and activates the iron oxide of Fe for the reaction, among which we can mention, by way of example, oxides inorganic selected from titania, zirconia, ceria, zinc oxide and combinations thereof, preferably
    15 titania. Iron oxide can be found either on the surface or in the network of the compatible solid. The amount of iron supported according to the process described in the present invention can range from 0.01 to 100 mol% of iron with respect to acetylene. For iron oxide nanoparticles in titania, the amounts are between 1 to 5 mol%.
    According to a particular embodiment, in the case of supported iron oxide, the catalyst can be prepared with sodium borohydride as a reducing agent, in one or two steps, or it can be prepared using hydrogen gas as a reducing agent. As we have already mentioned, according to a particular embodiment, the catalyst can
    25 be composed of iron oxide that are located in the network of compatible oxides, selected from titania, zirconia, ceria, zinc oxide and combinations thereof, preferably zirconia. Preferably, the network iron oxide catalyst can be prepared by co-precipitation and calcination.
    According to a particular embodiment of the present invention, the reaction temperature may be between 50 to 180 ° C, preferably between 100 to 160 ° C.
    image5
    According to a particular embodiment of the present invention, the reaction can be carried out under pressures between 1 and 20 bar.
    According to another particular embodiment of the present invention, the reaction can be carried out.
    5 carried out in a continuous fixed bed reactor, passing acetylene, ethylene and hydrogen, through a catalytic bed with the catalyst containing iron oxide, and at temperatures between 50 and 180 ° C and with a contact time between 0.1 and 4 h. The process can be carried out at pressures between 1 and 20 bars.
    The present invention also relates to the product obtained according to the procedure described above.
    Thus, the product is ethylene with a purity greater than 99.99%, which is considered sufficient for industrial polymerization.
    In addition, the present invention also relates to the use of the product obtained according to the process of the present invention. Preferably, the ethylene obtained serves as a monomer in the preparation of polyethylene (PE).
    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.
    25
    EXAMPLES
    Non-limiting examples of the present invention are detailed below:
    Example 1: Preparation of iron nanoparticles supported on compatible oxides, with NaBH4 as a reducing agent, in two steps.
    image6
    Step 1: In a 50 ml round bottom flask, 232 mg of FeCl2 is dissolved in 15 ml of distilled water, 50 mg of citric acid is added, and 120 mg of NaBH4 powder is added slowly under continuous magnetic stirring. During the addition, the generation of gas and the formation of a black solid are observed. When the generation
    5 of gases ceases, the solvent is decanted and the solid is washed several times with distilled water and dried under vacuum.
    Step 2: in a 500 ml round bottom flask containing a dispersion of 0.5 g of compatible solid in 12.5 ml of distilled water 50 mg of the black solid are added
    10 previously obtained under continuous magnetic stirring. After 18 hours, the solid is filtered off, washed several times with distilled water and dried under vacuum, at least 2 hours.
    Example 2: Preparation of iron nanoparticles supported on compatible oxides, with NaBH4 as a reducing agent, in a single step.
    2 grams of compatible solid and 25 ml of a solution in distilled water containing 387 mg of FeCl2 and 87 mg of citric acid are mixed in a 100 ml round bottom flask. 200 mg of NaBH4 are added in powder under continuous magnetic stirring.
    20 During the addition, the generation of gas and the progressive blackening of the solid are observed. After 18 hours, the solid is filtered off, washed several times with distilled water and dried under vacuum, at least 2 hours. The following table summarizes the amounts relative to other iron salts and percentages on the catalyst:
    Iron precursor Fe (% by weight)Mass to add (mg)NaBH4 (mg)
    FeSO47H2O 0.550.0412.00
    1.5 150.1236.00
    FeCl2  0.523.1612.00
    1.5 69.4936.00
    5 231.60120.00
    7 463.20240.00
    Faith (acac) 3  0.565.1922.35


    Example 3: Preparation of iron nanoparticles supported on compatible oxides, with H2 as reducing agent.
    5 2 grams of compatible solid and 25 ml of a solution in distilled water containing the corresponding iron precursor are mixed in a 100 ml round bottom flask (see table below for species and quantities). The mixture is stirred 12 hours at room temperature. The solvent is removed in vacuo and the solid is dried at 80 ° C and then treated under a stream of N2 at 550 ° C for 3.5 h, under a stream of air at 450
    10 ° C for 5 h and finally under N2 current at the same temperature. The reduction then occurs under a stream of hydrogen (100 ml / min) at 400 ° C for 3 h. The following table summarizes the amounts relative to other iron salts and percentages on the catalyst:
    Iron precursor Fe (% by weight)Mass to add (mg)
    FeSO47H2O 0.550.04
    1.5 150.12
    FeCl2 0.523.16
    1.5 69.48
    Faith (acac) 3  0.565.19
    fifteen
    Example 4: Preparation of iron oxide in a network of compatible oxides.
    In a 100 ml plastic beaker, the corresponding iron and titania or zirconia precursors are added at the same time, with paddle stirring
    20 continuous and at room temperature. The precipitated solid is filtered off, washed several times with distilled water and dried at 80 ° C in an oven, and finally calcined at 450 ° C.
    Example 5: Reaction procedure in a fixed bed reactor.
    25


    A mixture of hydrogen, acetylene and ethylene in the gas phase (0.4: 0.1: 10 ratio) was fed to a reactor with a fixed, solid catalyst tubular bed containing 1% by weight of iron oxide in titania or zirconia (50 mg ) at 160 ºC, with a contact time of 0.5-2 h. The reaction is followed by a GC device with FID detector, connected online. For 50 mg of catalyst, the conversion of acetylene is complete until 140 h of reaction, without any deactivation of the catalyst. Ethylene is the main product together with <0.01% ethane.
    权利要求:
    Claims (19)
    [1]
    image 1
    1. Ethylene stream purification process characterized in that it comprises at least the following steps:
    5
    - A first stage in which a stream of ethylene comprising at least acetylene and hydrogen is contacted with a catalyst containing iron oxide.
    - A second stage of heating the obtained mixture. 10 - A third stage of product recovery.
    [2]
    2.  Purification process of ethylene streams according to claim 1, characterized in that acetylene is selectively hydrogenated in the first stage against ethylene.
    [3]
    3.  Purification process of ethylene streams according to any one of claims 1 and 2, characterized in that the amount of acetylene containing the ethylene stream is in amounts between 20 ppm and pure acetylene.
    fifteen
    Method of purifying ethylene streams according to claim 3, characterized in that the amount of acetylene containing the ethylene stream is in amounts between 100-10000 ppm.
    [5]
    5. Ethylene stream purification procedure according to any of the
    The preceding claims, characterized in that the amount of hydrogen is 1 to 10 equivalents with respect to ethylene.
    [6]
    6. Ethylene stream purification process according to claim 5,
    characterized in that the amount of hydrogen is 1 to 3 equivalents with respect to ethylene.
    image2
    [7]
    7. Purification process of ethylene streams according to the preceding claims, characterized in that the ratio of acetylene to catalyst is between 10,000 and 10.
    Method of purifying ethylene streams according to the preceding claims, characterized in that an iron oxide catalyst is used.
    [9]
    9. Ethylene stream purification process according to claim 8,
    characterized in that a nanoparticulate iron oxide catalyst 10 supported on compatible solids is used.
    [10]
    10.  Purification process of ethylene streams according to claim 9, characterized in that the solid is an inorganic oxides selected from titania, zirconia, ceria, zinc oxide and combinations thereof.
    [11]
    eleven.  Purification process of ethylene streams according to claim 8 to 11, characterized in that the catalyst is composed of iron oxide nanoparticles supported in titania.
    fifteen
    Method of purifying ethylene streams according to any of claims 9 to 11, characterized in that the amount of iron supported ranges from
    [0]
    0.01 to 100% mol of iron with respect to acetylene.
    [13]
    13. Ethylene stream purification process according to any of the
    25 claims 9 to 12, characterized in that the catalyst is prepared with sodium borohydride as a reducing agent, in one or two steps.
    [14]
    14. Ethylene stream purification procedure according to any of the
    claims 9 to 12, characterized in that the catalyst is prepared with hydrogen gas as a reducing agent.
    image3
    [15]
    15. Method of purification of ethylene streams according to claim 8, characterized in that the catalyst is composed of iron oxide particles in a network of compatible oxides.
    16. Method of purifying ethylene streams according to claim 15, characterized in that the iron oxide catalyst is inserted into zirconia.
    [17]
    17. Ethylene stream purification process according to the claims
    15 and 16, characterized in that the catalyst with iron oxide in a network is prepared by co-precipitation and calcination.
    [18]
    18. Ethylene stream purification process according to the preceding claims, characterized in that the reaction temperature is set between 50 to 180 ° C.
    19. Method of purifying ethylene streams according to claim 18, characterized in that the reaction temperature is between 100 and 160 ° C.
    [20]
    20. Ethylene stream purification process according to any of the
    previous claims, characterized in that the reaction is carried out under pressures 20 of between 1 and 20 bar.
    [21]
    21. Method of purifying ethylene streams according to any of the preceding claims, characterized in that the reaction is carried out in a continuous fixed bed reactor.
    25
    [22]
    22. Method of purifying ethylene streams according to claim 21, characterized in that the current passes through a catalytic bed with the catalyst containing iron oxide, with a contact time between 0.1 and 4 h.
    23. Product obtained according to the procedure described in claims 1 to 22, characterized in that it is ethylene with a purity greater than 99.99%
    image4
    [24]
    24. Use of the product according to claim 23 obtained by the process described in claims 1 to 22 as a monomer for the preparation of polyethylene.
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    同族专利:
    公开号 | 公开日
    WO2018134455A1|2018-07-26|
    ES2680194B1|2019-06-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2775634A|1953-06-22|1956-12-25|Phillips Petroleum Co|Removal of acetylene from olefins by selective hydrogenation|
    US3243387A|1963-04-25|1966-03-29|Leuna Werke Veb|Palladium-silver-iron oxide on alphaalumina catalyst composition for the selective hydrogenation of acetylene|
    US3296325A|1963-12-11|1967-01-03|Chemetron Corp|Catalyst and method for producing the same|
    法律状态:
    2018-09-04| BA2A| Patent application published|Ref document number: 2680194 Country of ref document: ES Kind code of ref document: A1 Effective date: 20180904 |
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201730053A|ES2680194B1|2017-01-18|2017-01-18|SELECTIVE CATALYTIC HYDROGENATION OF ACETYLENE IN PRESENCE OF ETHYLENE EXCESS|ES201730053A| ES2680194B1|2017-01-18|2017-01-18|SELECTIVE CATALYTIC HYDROGENATION OF ACETYLENE IN PRESENCE OF ETHYLENE EXCESS|
    PCT/ES2018/070021| WO2018134455A1|2017-01-18|2018-01-11|Selective catalytic hydrogenation of acetylene in the presence of excess ethylene|
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