• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a double-layer-structured catalyst for dehydrogenation. The present invention provides a double-layered-structured catalyst for dehydrogenation, which is used in dehydrogenation reactions of light hydrocarbon gases in a range of C3 to C6 and has a form in which platinum, tin, and an alkali metal are supported on a phase-changed supporter, wherein the tin component exists throughout the inside of the supporter and platinum and tin exit in an alloy form, as a single complex form, within a predetermined thickness from the outside of the support.
    公开号:ES2803126A2
    申请号:ES202090060
    申请日:2019-05-17
    公开日:2021-01-22
    发明作者:Young-San Yoo；Hyun A Choi；Dong Kun Kang；Young Ho Lee
    申请人:Heesung Catalysts Corp；
    IPC主号:
    专利说明:

    [0002] Double-layer structured catalyst for dehydrogenating light hydrocarbons
    [0004] Technical field
    [0006] The present disclosure relates to a structured double layer catalyst for dehydrogenating light hydrocarbons and a method of making the same. More particularly, the present disclosure relates to a technology of a catalyst and a method of manufacturing the catalyst, wherein the catalyst contains two types of metal components in an alloy form present in a range of a predetermined thickness on a surface. of a catalyst carrier and one of the two kinds of metal components is distributed over an entire region of the catalyst, and the catalyst has high durability and high regeneration efficiency when used in the dehydrogenation of light hydrocarbons.
    [0008] Technical background
    [0010] A dehydrogenation of light hydrocarbons using a catalyst has advantages in that a product having high yield and high purity is obtained, and it is a reaction that has high production efficiency and simple process. Therefore, research related to the manufacture of light olefins by dehydrogenation using a catalyst has been ongoing continuously.
    [0012] The present applicant has disclosed a catalyst that shows improved selectivity and reactivity, and is suitable for use in the manufacture of an olefin by dehydrogenating C3, C4, or C9 to C13 paraffin. More in particular, a technology is used to manufacture a catalyst configured so that a heat-treated carrier having controlled pores and most of the metal components contained in the catalyst are uniformly distributed not in the form of individual metals, but in the form of an alloy on the carrier from the outer periphery or the entire region of the catalyst (Korean Patent Application Publication No. 10-2017-0054789, published May 18, 2017 and Korean Patent No. 10-176170, published on March 14, 2017). In the related art of a dehydrogenation catalyst, for active site control, since the intensity of platinum dehydrogenation is too strong, an alkali metal is introduced, and tin is introduced in an effort to prevent deterioration of the activity of the platinum. catalyst due to carbon deposit.
    [0013] Divulgation
    [0015] Technical problem
    [0017] According to the related art, there is a problem that since a catalyst is used in which platinum and tin in the form of an alloy are partially distributed on a portion of the outer surface or uniformly on an entire region of an alumina carrier, the activity of the catalyst decreases due to a situation that a carbon coke deposited on the alumina carrier covers an active site, and even when the coke is removed from the carrier using a calcination process, it is almost impossible to completely regenerate the catalyst at a initial state due to coke remaining therein.
    [0019] Technical solution
    [0021] In order to achieve the above objectives, according to one aspect of the present disclosure, a double layer structured catalyst is provided for use in the dehydrogenation of light hydrocarbon gas in a range of C3 to C6, configured so that platinum, tin, and an alkali metal that are transported in a phase-changed carrier, and the tin component is present in an entire region within the carrier, and the platinum and tin form a single complex and are present in a range of a predetermined thickness from an outer periphery of the carrier.
    [0023] In another embodiment of the present disclosure, the unique platinum-tin complex is formed in a range of 300 to 500 µm thickness from the outer periphery of the carrier, and the carrier can be selected from the group consisting of alumina. , silica, zeolite, and a complex component thereof.
    [0025] In the present disclosure, a catalyst for dehydrogenating a light paraffinic hydrocarbon actually looks the same as the related art in that a platinum and tin alloy in the carrier are present in a range of a predetermined thickness from the carrier surface to the inner core. However, it should be noted that, unlike the related art, the tin component in the catalyst of the present disclosure is uniformly distributed in the inner core. This new double-layer structure induces coke to form extensively within the carrier rather than just at the active site of dehydrogenation, thereby increasing durability and it also minimizes aging due to coke oxidation so that a catalyst can be provided that inhibits sintering of active metals.
    [0027] An objective of the present disclosure is to improve the efficiency of activation and regeneration under the influence of coke by placing coke inducing material in the center of the carrier in contrast to the related art which does not have an active metal in the inner core of the carrier.
    [0029] Advantageous effects
    [0031] In the catalyst having the double-layer structure according to the present disclosure, the tin component is uniformly present in the core of the carrier, while the platinum and tin in the form of an alloy are distributed in a range of a predetermined thickness within carrier. Here, the tin component distributed to the center or core of the carrier spreads the generation of the coke not only over the active site of the platinum-tin alloy, but also inside the carrier, thus minimizing the inactive phenomenon of platinum. produced by the generation of coke, and increasing the durability of the catalyst, while reducing the formation of coke in the active site, so that the aging of the catalyst is reduced and the sintering of platinum is prevented, whereby the improved catalyst regeneration.
    [0033] Description of the drawings
    [0035] Fig. 1 is a view schematically illustrating a structural difference of a catalyst that has been upgraded from conventional technology to a double-layer structured catalyst of the present disclosure;
    [0037] Figure 2 is a flow chart illustrating a manufacturing process for the double layer catalyst of the present disclosure;
    [0039] Figure 3 illustrates electron probe microanalysis (EPMA) images comparing a conventional technology catalyst (a) with a structured double layer catalyst of the present disclosure (b);
    [0040] Figure 4 illustrates electron microscopy (videomicroscopy) images comparing a state of a conventional technology catalyst with the double-layer structured catalyst of the present disclosure prior to regeneration.
    [0042] Best mode
    [0044] The present disclosure relates to a structured double layer catalyst for dehydrogenating light hydrocarbons and a method of making the same. More particularly, the present disclosure relates to a catalyst and catalyst method manufacturing, in which the catalyst contains two types of metal components, for example platinum and tin in an alloy form are present in a range of a thickness predetermined on a carrier surface, and one of the two types of metal components, for example, tin is distributed over an entire region of the catalyst, whereby the catalyst is improved in durability and regeneration efficiency when used in dehydrogenation of light hydrocarbons since the coke generation is distributed to the entire region of the carrier.
    [0046] From conventional technology, it has been noted that when the active metals of the light paraffinic hydrocarbon dehydrogenation catalyst are not distributed alone in the carrier but rather the active metals in the form of an alloy are present in a range of a predetermined thickness from the surface from the catalyst into the catalyst, it is possible to make a catalyst capable of greatly increasing the rate of paraffin conversion, olefin selectivity, and durability. However, there are still problems due to coke.
    [0048] In the present disclosure, the active metal of the catalyst refers to platinum, but exhaustively includes tin, and the double layer refers to a structure where the interior of the carrier is divided into two layers. For example, the alloy of platinum and tin is present in the outer layer, and the tin component is placed in the inner layer. The term 'double layer' is in contrast to a conventional technology structure that did not have any active components in the inner core. In the present disclosure, the term 'alloy' can be used interchangeably with the term 'complex'. The inner layer of the carrier can be referred to as the 'core', 'egg' or 'center', and the outer layer of the carrier can be referred to as the 'shell'. A thickness of the outer layer or a depth of the core can vary depending on the depth of the alloy. In other words, the thickness or depth of the outer and inner layers can vary depending on the depth of the alloy and is not fixed. In the present disclosure, the carrier can be selected from the group consisting of alumina, silica, zeolite, and a complex component thereof. Also, light hydrocarbon gas refers to light paraffin. More particularly, the light hydrocarbon gas is straight chain type or branched type hydrocarbons in a range from C3 to C6. The catalyst for the dehydrogenation of light hydrocarbons undergoes a reaction at a relatively high temperature compared with heavy hydrocarbons, thereby forming a large amount of coke due to thermal decomposition and other side reactions. However, surprisingly, the coke problem was solved by placing the tin component in the core of the related art dehydrogenation catalyst carrier. Specifically, the tin component placed to the center of the carrier extends the generation of coke not only to the active sites of the platinum-tin alloy, but also into the carrier, thereby improving the durability of the catalyst by minimizing a phenomenon platinum coating. Furthermore, by minimizing the generation of the coke at the active sites, the sintering phenomenon of platinum was prevented by reducing aging during the regeneration process, thereby realizing the improved regeneration efficiency of the catalyst. In other words, the density of the coke in the alloy of the active component decreases.
    [0050] In the present disclosure, a process of transporting the uniformly distributed tin in the carrier core is performed prior to transporting an active metal alloy complex, and the platinum and tin are formed in the complex in an organic solvent and transported simultaneously. with a certain amount of inorganic acids and / or a certain amount of organic acids, and distributing them in a range of a predetermined thickness on the surface of the carrier is done to complete the manufacture of the catalyst.
    [0052] Fig. 1 is a view schematically illustrating a structural difference of a catalyst that has been upgraded from conventional technology to a double-layer structured catalyst of the present disclosure. In a conventional technology dehydrogenation catalyst, platinum and tin form a single complex and are present in a range of a predetermined thickness from the outer periphery of the carrier. For example, platinum and tin are present in the shell as an alloy, while the dehydrogenation catalyst of the present disclosure has an egg-shell structure with a tin component uniformly added to the core of the carrier.
    [0053] FIG. 2 is a flow chart illustrating a manufacturing process of the double layer catalyst of the present disclosure, which comprehensively explains the method of the present disclosure.
    [0055] 1) Pre-treatment process with the tin precursor solution
    [0057] In order to increase pore size and pore volume, the carrier is heat treated in a calcination oven at 1000 to 1050 ° C for 1 to 5 hours, whereby the gamma alumina is phase changed to theta alumina before wearing the carrier. During the manufacture of the tin precursor, a certain amount of the tin precursor is mixed with an excessive amount of inorganic acid such as hydrochloric acid and nitric acid, and the mixture is placed in deionized water, where the excessive amount of the inorganic acid acts as a dual role that makes the melting of the tin precursors in the deionized water easy and ensures that the tin precursor reaches the core portion of the carrier. The carrier is placed in the produced tin precursor solution until the carrier is fully submerged, and the carrier is aged for 2 to 24 hours to allow the tin component to reach the core of the carrier, and then a process is performed filter to remove moisture from it mainly. After that, a drying process is carried out at 80 to 150 ° C for 24 hours, thus secondarily and completely eliminating the remaining moisture in the catalyst, and then a calcination process is carried out at 400 to 700 ° C in air. , thus obtaining a pretreated catalytic structure in which the tin is placed in the entire region thereof.
    [0059] 2) Stabilized platinum-tin compound solution manufacturing process
    [0061] The platinum-tin compound solution easily precipitates platinum in the air due to the high reducibility of tin. Therefore, the selection of a solvent is very important in the manufacture of the compounding solution. First, the platinum and tin precursors were added to the organic solvent so that the platinum-tin compound did not decompose when mixed with each other, and hydrochloric acid was added to produce an acidic solution. Next, an organic acid was added to the organic solvent in order to increase the penetration rate into the interior of the carrier. During the manufacture of the platinum-tin compound solution, the solution is kept in an atmosphere of an inert gas and decomposition by oxygen is suppressed whereby stabilization of the solution is achieved. Here, nitrogen, argon and helium can be used as the inert gas, and nitrogen gas is preferably used.
    [0062] 3) Manufacturing process of double layer structured catalyst using stabilized platinum-tin compound solution and alkali metal
    [0064] In the process of transporting the active metal alloy solution, a platinum-tin compound solution is manufactured in an amount equivalent to the total pore volume of the carrier, and impregnated into the carrier using a spray transportation method. After impregnation, an aging process is carried out for a predetermined period of time in order to control the depth of penetration of platinum and tin into alumina by an organic acid. After the aging process, a quick drying process is performed while fluidizing the catalyst in an atmosphere of 150 to 250 ° C, thus removing most of the organic solvent that remains on the catalyst. The remaining water on the catalyst is completely removed through a drying process at 100 to 150 ° C for 24 hours. The reason for rapid drying is to prevent the solution of the platinum-tin compound from diffusing into the carrier together with an inorganic or organic acid solvent over time when the solution of the platinum-tin compound is transported on the alumina carrier. in which the tin component is already placed. After drying, an organic material is removed in a nitrogen atmosphere of 250 to 400 ° C, followed by a calcination process in an ambient atmosphere of 400 to 700 ° C.
    [0066] After calcination, a process to transport alkali metal is carried out in order to suppress the side reaction of the catalyst. First, potassium is transported into the internal pores of the carrier using the same spray transport method as in the platinum-tin compound solution manufacturing process, and a drying process is carried out at 100 to 150 ° C for 24 hours, and a calcination process in an ambient atmosphere at a temperature in a range of 400 to 700 ° C. Finally, after calcination, a reduction process is carried out using a hydrogen / nitrogen gas mixture (a range of 4% / 96% to 100% / 0%) at a temperature in a range of 400 to 600 ° C, obtaining in this way a final catalyst.
    [0068] Electron probe microanalysis (EPMA) images of the double-layer catalyst manufactured by the method are shown in Figure 3b. Figure 3a illustrates an electron probe microanalysis (EPMA) image of a conventional technology catalyst, and Figure 3b illustrates an electron probe microanalysis (EPMA) image of a double-layer structured catalyst of the present disclosure . Carrier core The present disclosure has a uniformly distributed tin component, whereas there is no active metal component in the carrier core in conventional technology.
    [0070] After packing the structured double-layer catalyst made by the method of the present disclosure to a fixed-bed catalyst reactor, and then generating an olefin by the dehydrogenation reaction, it is observed whether or not a coating is formed inside the catalyst. Figure 4 illustrates electron microscopy (videomicroscopy) images comparing a state of a conventional technology catalyst with the double-layer catalyst of the present disclosure prior to regeneration. A coke deposit is observed in the core of the double-layer catalyst of the present disclosure as expected, while coke formation is suppressed in the conventional technology catalyst. Thus, the active site coke density of the catalyst is significantly lower for the double layer catalyst of the present disclosure, resulting in a substantial increase in durability and regeneration efficiency of the catalyst of the present disclosure.
    权利要求:
    Claims (4)
    [1]
    1. A structured double layer catalyst for use in the dehydrogenation of light hydrocarbon gas in a range of C 3 to C 6 , the catalyst comprising:
    platinum, tin, and an alkali metal that are transported in a phase-changed carrier,
    wherein the tin component is present in an entire region within the carrier, and the platinum and tin form a single complex and are present in an alloy form in a range of a predetermined thickness from an outer periphery of the carrier.
    [2]
    The catalyst according to claim 1, wherein the predetermined thickness from the outer periphery of the carrier is 300 to 500 µm thick.
    [3]
    3. The catalyst according to claim 1 or 2, wherein the alkali metal is selected from the group consisting of potassium, sodium and lithium.
    [4]
    The catalyst according to claim 1 or 2, wherein the carrier is selected from the group consisting of alumina, silica, zeolite, and a complex component thereof.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    KR890000516B1|1984-12-03|1989-03-20|유오피 인코퍼레이드|Indium-containing dehydrogenation catalyst|
    US4716143A|1986-06-06|1987-12-29|Uop Inc.|Dehydrogenation catalyst composition|
    JPH074529B2|1987-12-28|1995-01-25|ユーオーピーインコーポレイテッド|Layered catalyst particles for dehydrogenation reaction|
    KR101477413B1|2013-07-30|2014-12-29|삼성토탈 주식회사|Preparation method of Platinum/Tin/Metal/Alumina catalyst for direct dehydrogenation of n-Butane and method for producing C4 olefins using said catalyst|
    KR101562458B1|2014-04-04|2015-10-22|주식회사 효성|Preparation of dehydrogenation catalysts having superior selectivity|
    KR101716170B1|2015-11-10|2017-03-14|희성촉매 주식회사|A stabilized active metal complex based catalyst for dehydrogenation of light straight-chain hydrocarbons|
    KR101814451B1|2015-11-10|2018-01-04|희성촉매 주식회사|A stabilized active metal complex based catalyst for dehydrogenation of straight-chain hydrocarbons|
    法律状态:
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