WO2020106013A1 - Catalyseur pour réaction de déshydrogénation oxydante et son procédé de production - Google Patents

Catalyseur pour réaction de déshydrogénation oxydante et son procédé de production

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Publication number
WO2020106013A1
WO2020106013A1 PCT/KR2019/015836 KR2019015836W WO2020106013A1 WO 2020106013 A1 WO2020106013 A1 WO 2020106013A1 KR 2019015836 W KR2019015836 W KR 2019015836W WO 2020106013 A1 WO2020106013 A1 WO 2020106013A1
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WIPO (PCT)
Prior art keywords
catalyst
zinc ferrite
oxidative dehydrogenation
dehydrogenation reaction
based catalyst
Prior art date
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Ceased
Application number
PCT/KR2019/015836
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English (en)
Korean (ko)
Inventor
황예슬
고동현
이주혁
서명지
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LG Chem Ltd
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LG Chem Ltd
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Filing date
Publication date
Priority claimed from KR1020190147776A external-priority patent/KR102436310B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to CN201980008911.XA priority Critical patent/CN111655371B/zh
Priority to EP19887456.2A priority patent/EP3721996B1/fr
Priority to US16/963,639 priority patent/US11618012B2/en
Publication of WO2020106013A1 publication Critical patent/WO2020106013A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/12—Alkadienes
    • C07C11/16—Alkadienes with four carbon atoms
    • C07C11/167—1, 3-Butadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor

Definitions

  • the present application relates to a catalyst for an oxidative dehydrogenation reaction and a method for manufacturing the same.
  • the oxidative dehydrogenation reaction of butene to produce butadiene which is gradually increasing in demand, is a reaction in which butene and oxygen react to produce butadiene and water. In addition, it is possible to lower the reaction temperature.
  • the oxidative dehydrogenation reaction of normal-butene (1-butene, trans-2-butene, cis-2-butene) is a reaction in which normal-butene and oxygen react to produce butadiene and water.
  • oxygen is used as a reactant, many side reactions such as a complete oxidation reaction are expected. Therefore, it is the most important core technology to suppress such side reactions as much as possible and to develop a catalyst having a high selectivity of butadiene.
  • Catalysts used in the oxidative dehydrogenation reaction of butenes known to date include ferrite-based catalysts, tin-based catalysts, and bismuth molybdate-based catalysts.
  • the ferrite-based catalyst has a different activity as a catalyst depending on the type of metal constituting the divalent cation site of the spinel structure.
  • zinc ferrite, magnesium ferrite, and manganese ferrite have good activity in the oxidative dehydrogenation reaction of butene. It has been reported that zinc ferrite has a higher selectivity of butadiene than ferrite catalysts of other metals [F.-Y. Qiu, L.-T. Weng, E. Sham, P. Ruiz, B. Delmon, Appl. Catal., Vol. 51, p. 235 (1989)].
  • the oxidative dehydrogenation reaction is performed in an excess of 10 times the steam condition compared to butene, which lowers the partial pressure of butene to increase the explosive range. This is because it is known to increase the stability of the reactor by directly removing the reaction heat generated during the oxidative dehydrogenation reaction as well as the lowering role, and increase the conversion of butene and increase the selectivity to butadiene by acting directly on the catalyst surface.
  • This application intends to provide a catalyst for an oxidative dehydrogenation reaction and a method for manufacturing the same.
  • a core portion including a porous support and a first zinc ferrite-based catalyst supported on the porous support
  • the first zinc ferrite-based catalyst and the second zinc ferrite-based catalyst provide catalysts for oxidative dehydrogenation reactions that are different from each other.
  • the first zinc ferrite catalyst and the second zinc ferrite catalyst provide a method for preparing a catalyst for an oxidative dehydrogenation reaction, which is different from each other.
  • the catalyst for an oxidative dehydrogenation reaction according to an exemplary embodiment of the present application, by supporting two types of zinc ferrite-based catalysts on a porous support, suppresses side reactions due to introduction of metal components of the catalyst and low hot spot movement speed The two effects of can be introduced simultaneously without changing the structure of ferrite.
  • the catalyst for an oxidative dehydrogenation reaction can obtain butadiene with a high yield while using a small amount of steam.
  • the catalyst for an oxidative dehydrogenation reaction can obtain a high 1,3-butadiene yield compared to a conventional zinc ferrite-based catalyst used for oxidative dehydrogenation of butene, and at the same time It may have a low hot spot movement speed.
  • FIG. 1 is a view schematically showing a manufacturing process of a catalyst for an oxidative dehydrogenation reaction according to an exemplary embodiment of the present application.
  • FIG. 2 is a view schematically showing a manufacturing process of a catalyst for a conventional oxidative dehydrogenation reaction.
  • 'yield (%)' is defined as a value obtained by dividing the number of moles of 1,3-butadiene as a product of an oxidative dehydrogenation reaction by the number of moles of butene as a raw material.
  • the yield can be expressed by the following equation.
  • 'conversion rate (%)' refers to a rate of conversion of a reactant to a product.
  • the conversion rate of butene may be defined by the following equation.
  • 'selectivity (%)' is defined as a value obtained by dividing the amount of change in butadiene (BD) by the amount of change in butene (BE).
  • the selectivity can be expressed by the following equation.
  • 'butadiene' means 1,3-butadiene.
  • a ferrite-based catalyst is mainly used for the production reaction of butadiene through an oxidative dehydrogenation reaction of butene. It is known that the zinc ferrite catalyst has the highest activity among the ferrite catalysts.
  • the zinc ferrite-based catalyst forms a spinel structure having the chemical formula of ZnFe 2 O 4 in theory, and an additional function may be added to the catalyst using a method of adding a metal other than Zn and Fe.
  • a metal is additionally added to the zinc ferrite catalyst, a phenomenon in which an intrinsic crystal structure of the zinc ferrite catalyst changes occurs, which may lead to a decrease in catalyst performance.
  • the present inventors conducted a study on a catalyst including two or more types of a metal-added zinc ferrite catalyst, a metal-free pure zinc ferrite catalyst, and the like, and completed the present invention.
  • a catalyst for an oxidative dehydrogenation reaction includes a porous support, and a core portion including a first zinc ferrite-based catalyst supported on the porous support; And a shell portion including a second zinc ferrite-based catalyst supported on the core portion, wherein the first zinc ferrite-based catalyst and the second zinc ferrite-based catalyst are different from each other.
  • the first zinc ferrite-based catalyst and the second zinc ferrite-based catalyst may be independently represented by any one of the following Chemical Formulas 1 to 3. However, at this time, the first zinc ferrite catalyst and the second zinc ferrite catalyst are different from each other.
  • R1 and R2 are each independently Cs, Ti, Zr, V, Nb, W, Cu, Ag, Cd, Sb, Ce, Cr, Mn, K, Co or Mo, provided that R1 and R2 are different from each other,
  • x is each independently 1 to 2.8
  • y and y ' are each independently 1 to 6,
  • a, b, c, a ', b' and c ' are each independently 0 to 2.8 or less.
  • the first zinc ferrite-based catalyst may be represented by the following Chemical Formula 1
  • the second zinc ferrite-based catalyst may be represented by the following Chemical Formula 2.
  • the second zinc ferrite-based catalyst may be represented by Formula 1 below, and the first zinc ferrite-based catalyst may be represented by Formula 2 below.
  • the first zinc ferrite-based catalyst may be represented by the following Chemical Formula 2
  • the second zinc ferrite-based catalyst may be represented by the following Chemical Formula 3.
  • different catalysts are intended to be supported on the inside and the outside of the porous support, respectively. That is, a core part was formed by supporting a first zinc ferrite catalyst inside the porous support, and a second zinc ferrite catalyst different from the first zinc ferrite catalyst was formed on the outside of the porous support to form a shell. Accordingly, a side reaction can be suppressed, and a catalyst for an oxidative dehydrogenation reaction having a low hot spot movement speed can be provided.
  • the first zinc ferrite-based catalyst may be supported on the inside of the porous support, and the second zinc ferrite-based catalyst may be supported on the outermost surface of the porous support.
  • the content of the first zinc ferrite-based catalyst may be 5% to 40% by weight, and 15% to 30% by weight %.
  • process cost due to an increase in reaction temperature may increase, and when it exceeds 40% by weight, COx selectivity increases and conversion decreases due to an increase in exotherm of the catalyst Can occur.
  • the content of the second zinc ferrite-based catalyst may be 0.1% to 30% by weight, and 10% to 20% by weight %.
  • the content of the second zinc ferrite-based catalyst is less than 0.1% by weight, an effect cannot be obtained compared to the case where the second zinc ferrite-based catalyst is not introduced, and when it exceeds 30% by weight, the catalyst during the manufacturing process due to abrasion Can cause loss.
  • the catalyst for the oxidative dehydrogenation reaction may further include an organic binder in addition to the first zinc ferrite-based catalyst and the second zinc ferrite-based catalyst.
  • the organic binder may be ethyl cellulose, methyl cellulose, or a derivative thereof, preferably methyl cellulose, but is not limited thereto.
  • the organic binder can improve the coatability and formability of the catalyst, and alleviate crack formation in the drying step during the catalyst manufacturing process.
  • the porous support may include a plurality of pores formed on the inside and the surface thereof, wherein the porosity of the porous support is 70% by volume or less, specifically, 50% by volume or less , More specifically, may be 30% by volume or less.
  • the porosity of the porous support exceeds 70% by volume, a catalyst supported in any region inside the porous support cannot participate in the reaction, and unnecessary side reactions may occur because it is difficult to disperse the exothermic heat between reactions.
  • the shape of the porous support is not particularly limited, but may include one or more of spherical, cylindrical, annular, and plate-shaped.
  • the porous support may include one or more of alumina, silica, zirconia, silicon carbide, and cordierite, and specifically, alumina.
  • a method of manufacturing a catalyst for an oxidative dehydrogenation reaction includes the steps of forming a core portion by supporting a first zinc ferrite catalyst on a porous support; And forming a shell portion by supporting a second zinc ferrite catalyst on the core portion, and the first zinc ferrite catalyst and the second zinc ferrite catalyst are different from each other.
  • the contents of the first zinc ferrite catalyst, the second zinc ferrite catalyst, and the porous support are the same as described above.
  • the method for preparing a catalyst for an oxidative dehydrogenation reaction may further include preparing each of the first zinc ferrite-based catalyst and the second zinc ferrite-based catalyst.
  • the first zinc ferrite-based catalyst and the second zinc ferrite-based catalyst may be represented by any one of Chemical Formulas 1 to 3 as described above, and a method for preparing a zinc ferrite-based catalyst known in the art may be used.
  • the zinc ferrite-based catalyst represented by Chemical Formula 1 may include a step of contacting a metal precursor solution including a zinc precursor, a ferrite precursor, and water with a basic aqueous solution to obtain a precipitate; And after filtering the precipitate, it may include a step of drying and firing.
  • the zinc precursor and the ferrite precursor are each independently selected from the group consisting of nitrate, ammonium salt, sulfate, and chloride, or one or more types, or Hydrates thereof. Specifically, it is preferably nitrate or chloride, or a hydrate thereof.
  • the zinc precursor may be zinc chloride (ZnCl 2 ).
  • ZnCl 2 zinc chloride
  • the formation of a zinc ferrite catalyst is excellent.
  • the ferrite precursor may be ferric chloride (FeCl 3 ).
  • FeCl 3 ferric chloride
  • the formation of a zinc ferrite catalyst is excellent.
  • the water may be pure water (DI water), distilled water, or the like.
  • the temperature of the water may be more than 0 °C 40 °C. Preferably it may be more than 0 °C 30 °C or less. More preferably, it may be 5 ° C or more and 25 ° C or less.
  • the pH of the basic aqueous solution may be 7 to 10.
  • the pH may be 7.5 to 9.
  • the basic aqueous solution may be at least one selected from the group consisting of potassium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, aqueous sodium hydroxide solution, aqueous sodium carbonate solution and aqueous ammonia.
  • the basic aqueous solution may be ammonia water.
  • the concentration of the basic aqueous solution may be 20% to 40% by weight, and may be 25% to 30% by weight.
  • the step of obtaining the precipitate may further include agitating the metal precursor solution after contacting the basic aqueous solution.
  • the stirring step may be performed at room temperature, and the stirring method may be used without limitation as long as it is a method of mixing a liquid phase and a liquid phase.
  • the stirring time of the stirring step may be 30 minutes to 3 hours, and may be 1 hour to 2 hours.
  • the step of filtering the precipitate is not particularly limited as long as it is a filtration method commonly used in the art.
  • it may be vacuum filtration.
  • it may be a method of filtering under reduced pressure using a vacuum pump, and in this case, there is an effect of washing and separating moisture from the catalyst.
  • the precipitate may be further filtered and washed before firing. By further including the washing step, it is possible to remove unnecessary ions (ions) remaining in the precipitate.
  • the drying step may be performed after filtration and washing after filtering the precipitate.
  • the step of drying the precipitate is not particularly limited as long as it is a drying method commonly used in the art. For example, a dryer can be used and an oven can be used.
  • the drying step may be dried at 80 °C to 150 °C.
  • the step of calcining the precipitate may be heated at a rate of 1 ° C / min at 80 ° C, and maintained at 600 ° C to 800 ° C for 5 to 10 hours.
  • the calcination step specifically, 600 °C to 700 °C, may be specifically baked at 600 °C to 650 °C.
  • the calcining step may be specifically 5 to 8 hours, and more specifically 5 to 6 hours.
  • the firing method may be a heat treatment method commonly used in the art.
  • the step of calcining the precipitate may be performed by injecting 1 L / min of air into the kiln.
  • a method for preparing a catalyst for an oxidative dehydrogenation reaction includes forming a core portion by supporting a first zinc ferrite-based catalyst on a porous support.
  • the step of supporting the first zinc ferrite-based catalyst on the porous support to form a core portion may include coating the first zinc ferrite-based catalyst on the entire inner and outermost surfaces of the porous support.
  • the method of manufacturing a catalyst for an oxidative dehydrogenation reaction includes forming a shell portion by supporting a second zinc ferrite-based catalyst on the core portion.
  • the step of supporting the second zinc ferrite-based catalyst on the core portion to form a shell portion includes: removing the first zinc ferrite-based catalyst provided on the outermost surface of the porous support; And coating the second zinc ferrite catalyst on the outermost surface of the porous support.
  • the step of removing the first zinc ferrite-based catalyst provided on the outermost surface of the porous support is based on the total weight of the coated first zinc ferrite-based catalyst, the removal It can be carried out until the amount of the first zinc ferrite-based catalyst is 0.1% by weight to 5% by weight, it can be performed until 0.15% by weight to 4.5% by weight.
  • the amount of the first zinc ferrite-based catalyst to be removed is less than 0.1% by weight, loss due to abrasion may occur during the supporting process of the second zinc ferrite-based catalyst, and when it exceeds 5% by weight, the first zinc ferrite-based catalyst
  • the removal amount of the catalyst may increase, and thus the manufacturing cost of the catalyst may increase.
  • a method of removing the first zinc ferrite-based catalyst provided on the outermost surface of the porous support, 10 minutes after putting the catalyst having the first zinc ferrite-based catalyst in a 100 ⁇ m sieve It may be performed by applying a vibration to the sieve for about 1 hour. For example, if the sieve is performed for 10 minutes, about 0.1% by weight may be removed.
  • the manufacturing process of the catalyst for an oxidative dehydrogenation reaction according to an exemplary embodiment of the present application is schematically illustrated in FIG. 1, and the conventional manufacturing process of a catalyst for an oxidative dehydrogenation reaction is schematically illustrated in FIG. 2.
  • the first zinc ferrite-based catalyst may be supported on the inside of the porous support, and the second zinc ferrite-based catalyst may be on the outermost surface of the porous support. It can be carried.
  • an exemplary embodiment of the present application preparing a catalyst for the oxidative dehydrogenation reaction; And using the catalyst for the oxidative dehydrogenation reaction in an oxidative dehydrogenation reaction of butene to provide butadiene.
  • the step of manufacturing the butadiene comprises a reaction temperature of 250 ° C. to 500 ° C. for a raw material comprising C4 oil, steam, oxygen (O 2 ) and nitrogen (N 2 ), At a pressure of 0.1 bar to 10 bar, it may be to react under the conditions of GHSV (Gas Hourly Space Velocity) 100h -1 to 400h -1 .
  • GHSV Gas Hourly Space Velocity
  • the C4 oil may mean useful C4 raffinate-1, 2, 3 after separating useful compounds from the C4 mixture produced by naphtha cracking, and refers to C4 species obtained through ethylene dimerization. It may be.
  • the C4 oil is n-butane (n-butane), trans-2-butene (trans-2-butene), cis-2-butene (cis-2-butene), and 1 It may be a mixture of 1 or 2 or more selected from the group consisting of -butene.
  • the steam (steam) or nitrogen (N 2 ) in the oxidative dehydrogenation reaction while reducing the risk of explosion of the reactant, while preventing the coking of the catalyst (coking) and removal of the reaction heat It is a dilution gas injected for the purpose.
  • the oxygen (O 2 ) reacts with a C4 fraction as an oxidant to cause a dehydrogenation reaction.
  • the oxidative dehydrogenation reaction may be prepared according to Scheme 1 or Scheme 2 below.
  • Butadiene is produced by removing hydrogen from butane or butene through the oxidative dehydrogenation reaction. Meanwhile, in the oxidative dehydrogenation reaction, a side reaction product including carbon monoxide (CO) or carbon dioxide (CO 2 ) may be generated in addition to the main reaction as in Reaction Scheme 1 or 2.
  • the side reaction product may include a process that is separated and discharged outside the system so that continuous accumulation does not occur in the process.
  • the conversion rate of butene may be 72% or more, preferably 72.5% or more, and more preferably 79% or more.
  • the selectivity of butadiene may be 85% or more, preferably 85.8% or more, and more preferably 87% or more.
  • the catalyst for an oxidative dehydrogenation reaction has two types of zinc ferrite catalysts supported on a porous support, thereby suppressing side reactions due to introduction of metal components of the catalyst and low hot spots ( hot spot) Two effects of moving speed can be introduced simultaneously without changing the structure of ferrite.
  • the catalyst for an oxidative dehydrogenation reaction can obtain butadiene with a high yield while using a small amount of steam.
  • the catalyst for an oxidative dehydrogenation reaction can obtain a high 1,3-butadiene yield compared to a conventional zinc ferrite-based catalyst used for oxidative dehydrogenation of butene, and at the same time It may have a low hot spot movement speed.
  • ZnFe 2 O 4 zinc-iron oxide
  • the prepared metal oxide powder was crushed to 0.6 mm to 0.85 mm and diluted in a weight ratio of 1: 1 in water to prepare a catalyst slurry. If necessary, a binder for increasing strength can be added to the catalyst slurry.
  • the porous aluminum silicate support was dipped in the prepared catalyst slurry, aerated and dried at 120 ° C. for 1 hour. Thereafter, the dried porous aluminum silicate support was immersed again in the catalyst slurry, aerated and dried three times.
  • the catalyst thus obtained was dried at 120 ° C. for 16 hours, heated to 80 ° C. at 1 ° C./min at a heating rate of 1 ° C./min under an air atmosphere, and then maintained for 6 hours for an oxidative dehydrogenation reaction having a porous structure. Catalysts were prepared.
  • Comparative Example 1 a catalyst for an oxidative dehydrogenation reaction was prepared in the same manner as in Comparative Example 1, except that 0.35 g of manganese chloride (MnCl 2 ⁇ 4H 2 O) was additionally added when preparing the metal precursor solution. Did.
  • Comparative Example 1 the oxidative dehydrogenation reaction was performed in the same manner as in Comparative Example 1, except that 0.35 g of chromium nitrate (Cr (NO 3 ) 3 ⁇ 9H 2 O) was additionally added when preparing the metal precursor solution. A catalyst was prepared.
  • the prepared metal oxide powder was crushed to 0.6 mm to 0.85 mm and diluted in a weight ratio of 1: 1 in water to prepare a first zinc ferrite catalyst slurry. If necessary, a binder for increasing strength can be added to the catalyst slurry.
  • the porous aluminum silicate support was immersed in the prepared first zinc ferrite catalyst slurry, aerated and dried at 120 ° C. for 1 hour. Thereafter, the dried porous aluminum silicate support was immersed again in the first zinc ferrite catalyst slurry, aerated and dried three times. The catalyst thus obtained was dried at 120 ° C. for 16 hours.
  • the prepared zinc-iron-chromium oxide powder was crushed to 0.6 mm to 0.85 mm, diluted in a weight ratio of 1: 1 in water to prepare a second zinc ferrite catalyst slurry.
  • the porous aluminum silicate support from which the first zinc ferrite catalyst was removed on the outermost surface was immersed in the prepared second zinc ferrite catalyst slurry, aerated and dried at 120 ° C. for 1 hour. Thereafter, the dried porous aluminum silicate support was immersed again in a second zinc ferrite-based catalyst slurry, aerated and dried three times.
  • the catalyst thus obtained was dried at 120 ° C. for 16 hours to prepare a catalyst for an oxidative dehydrogenation reaction having a porous structure.
  • the content analysis of Fe, Zn, Mn, Cr, etc. in the catalyst for the oxidative dehydrogenation reaction prepared in the above Examples and Comparative Examples can be performed using ICP (Inductively Coupled Plasma) analysis.
  • the ICP analysis can be measured using ICP-OES (inductively coupled plasma-optical emission) equipment. More specifically, an ICP-OES (Optima 7300DV) device may be used, and the sequence is as follows.
  • the sample is carbonized by heating it on a hot plate.
  • a catalyst for an oxidative dehydrogenation reaction prepared in each of the above Examples and Comparative Examples was fixed to a catalyst tube volume of 150 cc in a metal tubular reactor having a diameter of 1.8 cm, and cis-2-butene 40% by weight, trans-2- as a reactant
  • a butene mixture of 60% by weight of butene and oxygen were used, and nitrogen and steam were introduced.
  • the reactant ratio was set at a molar ratio of oxygen / butene 0.67, steam / butene 5 and nitrogen / butene 2.67, and steam was vaporized in a water vaporizer at 360 ° C. to enter the reactor together with the reactants.
  • the amount of the butene mixture was controlled to 0.625 cc / min using a mass flow regulator for liquids, oxygen and nitrogen were controlled using a mass flow regulator for gases, and the amount of steam was controlled using a liquid pump.
  • the gas hourly space velocity (GHSV) of the reactor was set to 120 h ⁇ 1 and reacted under normal pressure (pressure gauge 0) under the temperature conditions shown in Table 1 below.
  • GC gas chromatography
  • the catalyst for an oxidative dehydrogenation reaction is supported by two types of zinc ferrite catalysts on a porous support, thereby suppressing side reactions due to introduction of metal components of the catalyst and low hot spots ( hot spot) Two effects of moving speed can be introduced simultaneously without changing the structure of ferrite.
  • the catalyst for an oxidative dehydrogenation reaction can obtain butadiene with a high yield while using a small amount of steam.
  • the catalyst for an oxidative dehydrogenation reaction can obtain a high 1,3-butadiene yield compared to a conventional zinc ferrite-based catalyst used for oxidative dehydrogenation of butene, and at the same time It may have a low hot spot movement speed.

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Abstract

Selon un mode de réalisation, la présente invention concerne un catalyseur pour une réaction de déshydrogénation oxydante, comprenant : un support poreux ; une partie noyau supportée sur le support poreux et contenant un premier catalyseur à base de ferrite de zinc ; et une partie coque supportée sur la partie noyau et contenant un second catalyseur à base de ferrite de zinc, le premier catalyseur à base de ferrite de zinc et le second catalyseur à base de ferrite de zinc étant différents l'un de l'autre.
PCT/KR2019/015836 2018-11-19 2019-11-19 Catalyseur pour réaction de déshydrogénation oxydante et son procédé de production Ceased WO2020106013A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201980008911.XA CN111655371B (zh) 2018-11-19 2019-11-19 用于氧化脱氢反应的催化剂及其制备方法
EP19887456.2A EP3721996B1 (fr) 2018-11-19 2019-11-19 Catalyseur pour réaction de déshydrogénation oxydante et son procédé de production
US16/963,639 US11618012B2 (en) 2018-11-19 2019-11-19 Catalyst for oxidative dehydrogenation reaction, and method for producing same

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KR20180142601 2018-11-19
KR10-2018-0142601 2018-11-19
KR10-2019-0147776 2019-11-18
KR1020190147776A KR102436310B1 (ko) 2018-11-19 2019-11-18 산화적 탈수소화 반응용 촉매 및 이의 제조방법

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CN115703073B (zh) * 2021-08-12 2024-04-12 中国石油大学(华东) 一种金属氧化物@分子筛核壳型氧载体在低碳烷烃化学链脱氢耦合氢气选择性氧化过程中的应用

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