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WO2009045002A1 - Procédé permettant de préparer des catalyseurs à base de ferrite de zinc au moyen d'une solution tampon et procédé permettant de préparer du 1,3-butadiène au moyen de ces catalyseurs - Google Patents

Procédé permettant de préparer des catalyseurs à base de ferrite de zinc au moyen d'une solution tampon et procédé permettant de préparer du 1,3-butadiène au moyen de ces catalyseurs Download PDF

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WO2009045002A1
WO2009045002A1 PCT/KR2008/005095 KR2008005095W WO2009045002A1 WO 2009045002 A1 WO2009045002 A1 WO 2009045002A1 KR 2008005095 W KR2008005095 W KR 2008005095W WO 2009045002 A1 WO2009045002 A1 WO 2009045002A1
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Prior art keywords
butadiene
zinc ferrite
butene
catalyst
solution
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Inventor
Young Min Chung
Tae Jin Kim
Seong Jun Lee
Yong Seung Kim
Seung Hoon Oh
In Kyu Song
Hee Soo Kim
Ji Chul Jung
Ho Won Lee
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SK Energy Co Ltd
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SK Energy Co Ltd
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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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of 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
    • 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
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury

Definitions

  • the present invention relates to a method of preparing a zinc ferrite catalyst using a buffer solution and a method of producing 1,3-butadiene using the zinc ferrite catalyst, and, more particularly, to a method of preparing a zinc ferrite catalyst through a precipitation process in a state in which pH of a coprecipitation solution is constantly maintained using a buffer solution as a coprecipitation medium, and a method of producing 1,3-butadiene using the zinc ferrite catalyst, in which high value-added 1,3-butadiene can be produced by the oxidative dehydrogenation of a cheap C4 mixture including impurities, such as n-butene, n-butane and the like, on the zinc ferrite catalyst.
  • a cheap C4 mixture including impurities, such as n-butene, n-butane and the like
  • Methods of producing 1,3-butadiene largely may include naphtha cracking, direct dehydrogenation of n-butene, and oxidative dehydrogenation of n-butene.
  • Most commercially available 1,3-butadiene is chiefly produced through a naphtha cracking process. It is known that the supply of 1 ,3-butadiene produced through a naphtha cracking process accounts for 90% or more of the total supply thereof. Therefore, the supply and demand of 1,3-butadiene is greatly influenced by the capacity of a naphtha cracker.
  • a naphtha cracking process cannot solve the unbalance of supply and demand of 1,3-butadiene due to the increased demand for 1,3-butadiene, because a new naphtha cracker must be installed to meet the increased demand for 1,3-butadiene, and also because the naphtha cracking process is not an independent process performed only to produce only butadiene, so that when the production of 1,3-butadiene is increased through the enlargement of a naphtha cracker, other basic fractions besides 1,3- butadiene are excessively produced.
  • a dehydrogenation reaction in which 1,3-butadiene is obtained by detaching hydrogen from n- butene has lately attracted considerable attention as an alternative method of producing 1,3- butadiene.
  • the dehydrogenation reaction of n-butene includes a direct dehydrogenation reaction and an oxidative dehydrogenation reaction.
  • n-butene Since the direct dehydrogenation reaction of n-butene is an endothermic reaction, it requires high-temperature reaction conditions and thermodynamic low-pressure reaction conditions, and thus the yield of 1,3-butadiene is very low, so that it is not suitable as a commercial process [L.M. Madeira, M.F. Portela, Catal. Rev., volume 44, page 247 (2002)].
  • the oxidative dehydrogenation reaction of n-butene is a reaction obtaining 1,3- butadiene and water by reacting n-butene with oxygen. Since water is formed after the oxidative dehydrogenation reaction of n-butene is completed, the reaction is thermodynamically advantageous, and since the formed water serves to decrease the temperature of a reactor, the rapid change in the temperature of a catalyst layer can be prevented. Therefore, when a process of producing 1,3-butadiene at high efficiency through the oxidative dehydrogenation reaction of n-butene instead of naphtha cracking or direct dehydrogenation is developed, this process can be an efficient alternative process of independently producing 1,3-butadiene.
  • a C4 raffinate- 3 mixture or a C4 mixture can be practically used as a supply source of n-butene, and thus a cheap surplus C4 fraction can be made into high value-added products.
  • the C4 raffinate-3 mixture used in the present invention is a cheap C4 fraction obtained by sequentially separating 1,3 -butadiene, iso-butylene and 1-butene from the C4 mixture produced through naphtha cracking, and includes 2-butene (trans-2-butene or cis-2-butene), n-butane and 1-butene.
  • the oxidative dehydrogenation reaction of n-butene is a reaction of producing 1,3-butadiene and water from oxygen and n- butene. Since the oxidative dehydrogenation reaction of n-butene is thermodynamically advantageous compared to the direct dehydrogenation reaction of n-butene, 1,3-butadiene can be obtained in high yield even under moderate reaction conditions. However, in the oxidative dehydrogenation reaction of n-butene, oxygen is used as a reactant, and thus it is expected that many side reactions, such as a perfect oxidation reaction and the like, occur.
  • Examples of catalysts known to be efficiently used to produce 1,3- butadiene through the oxidative dehydrogenation of n-butene include Ferrite-based catalysts [M.A. Gibson, J.W. Hightower, J. Catal, volume 41, page 420 (1976) / W.R. Cares, J.W. Hightower, J. Catal, volume 23, page 193 (1971) / RJ. Rennard, W.L. Kehl, J. Catal, volume 21, page 282 (1971)], tin-based catalysts [Y.M. Bakshi, R.N. Gur'yanova, A.N. Mal'yan, A.I.
  • the ferrite-based catalyst has a spinel structure.
  • This spinel-structured ferrite has an oxidation number of 2 or 3, and can be practically used as a catalyst for an oxidative dehydrogenation reaction for producing 1,3- butadiene from n-butene through the oxidation-reduction of iron ions and the interaction between oxygen ions in crystal and oxygen gases [M.A. Gibson, J.W. Hightower, J. Catal., volume 41, page 420 (1976) / RJ. Rennard, W.L. Kehl, J. Catal., volume 21, page 282 (1971)].
  • the catalytic activities of ferrite catalysts as oxidative dehydrogenation reaction catalysts are different from each other depending on the kinds of metals constituting two- valence cation sites in a spinel structure. It is known that, among the ferrite catalysts, zinc ferrite, magnesium ferrite and manganese ferrite exhibit good activity to the oxidative dehydrogenation reaction of n-butene, and, particularly, it is reported that zinc ferrite exhibits higher 1,3-butadiene selectivity than other ferrite catalysts [F.-Y. Qiu, L.-T. Weng, E. Sham, P. Ruiz, B. Delmon, Appl. Catal., volume 51, page 235 (1989)].
  • Zinc ferrite acting as a main component in the oxidative dehydrogenation of n-butene, is chiefly prepared by a coprecipitation method.
  • a typical example of these methods is a method of adding zinc precursor and iron precursors to an excess aqueous basic reductant solution [LJ. Crose, L. Bajars, M. Gabliks, U.S patent No. 3,743,683 (1973) / J.R. Baker, U.S patent No. 3,951,869 (1976)].
  • n-butene when a multi-component catalyst, such as a zinc ferrite catalyst substituted with metal, a mixed phase catalyst or the like, is used, 1,3 -butadiene can be obtained in high yield compared to when a conventional zinc ferrite catalyst is used.
  • the multi-component catalyst since the multi-component catalyst includes various components, it is difficult to reproduce the multi-component catalyst, and thus the multi- component catalyst cannot be easily used as a catalyst for commercial use.
  • a C4 mixture which is a reactant used in the present invention, includes various C4 compounds in addition to n-butene, side reactions can occur in the above catalyst system including various components, and thus the activity of a catalyst and the selectivity of 1,3-butadiene may be worsened.
  • n-butane one of the problems occurring in the oxidative dehydrogenation process of n-butene is that, when the reactant passing through a catalyst layer includes n-butane at a predetermined amount or more, catalytic activity is decreased, and thus the yield of 1,3-butadiene is decreased [L.M. Welch, LJ. Croce, H.F. Christmann, Hydrocarbon Processing, page 131 (1978)]. Therefore, in the conventional technologies, in order to solve the above problems, pure n-butene (1-butene or 2-butene) is separated from a C4 mixture and then used as a reactant, and, even in commercial processes in which a ferrite catalyst is really used, a reactant from which n-butane is removed is used.
  • a pure single-phase zinc ferrite catalyst can be prepared in a coprecipitation solution having a constant pH using a buffer solution through a coprecipitation process, and mat, when this prepared zinc ferrite catalyst is used, 1,3-butadiene can be produced in high yield using a cheap C4 mixture including n-butane and n-butene as a reactant through an oxidative dehydrogenation reaction without performing an additional n-butene separation process.
  • an object of the present invention is to provide a method of preparing a zinc ferrite catalyst for producing 1,3-butadiene, having a simple structure, a simple synthesis path and excellent reproducibility.
  • Another object of the present invention is to provide a method of producing 1,3- butadiene by directly using a C4 mixture as a reactant through an oxidative dehydrogenation reaction on the prepared zinc ferrite catalyst without performing an additional n-butene separation process.
  • an aspect of the present invention provides a zinc ferrite catalyst for producing 1,3-butadiene, including pure single-phase zinc ferrite prepared using a buffer solution having a pH of 6 ⁇ 12 as a coprecipitation medium.
  • another aspect of the present invention provides a method of preparing a zinc ferrite catalyst for producing 1,3-butadiene, including: a) dissolving a zinc precursor and an iron precursor in distilled water in a predetermined amount to form a precursor solution; b) preparing a buffer solution having a predetermined pH range; c) dropping the precursor solution into the buffering solution to coprecipitate zinc ferrite; d) filtering the mixed solution of the buffer solution and precursor solution to obtain a solid precipitate and then drying the solid precipitate at a temperature of 70 ⁇ 200 " C ; and e) heat- treating the dried solid precipitate at a temperature of 350 ⁇ 800 ° C to obtain a zinc ferrite catalyst.
  • a further aspect of the present invention provides a method of producing 1,3-butadiene through the oxidative dehydrogenation reaction of a C4 mixture including n-butene and n-butane using the zinc ferrite catalyst prepared by injecting precursors into a buffer solution having a pH of 6 ⁇ 12 through a coprecipitation process.
  • a zinc ferrite catalyst having a simple structure, a simple synthesis path and excellent reproducibility can be prepared through a simple process of injecting an aqueous precursor solution into a buffer solution, and thus the zinc ferrite catalyst can be easily and rapidly prepared compared to when it is prepared through a conventional coprecipitation process.
  • the conversion ratio of n-butene and the yield of 1,3-butadiene can be increased even when a C4 mixture including highly-concentrated n-butane is used as a reactant for an oxidative dehydrogenation reaction without performing an additional process of removing n-butane from the C4 mixture or separating n-butene from the C4 mixture, so that the expenses taken to perform the process of removing n-butane from the C4 mixture or separating n-butene from the C4 mixture can be avoided, thereby greatly improving the economical efficiency of the 1,3- butadiene preparation process.
  • 1,3 -butadiene having high use value in the petrochemical industries can be directly produced from a C4 mixture or C4 raffinate-3 having low use value
  • a C4 mixture can be made into a high value-added product.
  • 1,3 -butadiene can be independently produced without installing a new naphtha cracker, the demand for 1,3-butadiene can be satisfied, so that economical profits can be obtained, thereby actively coping with changes in the market in the future.
  • FIG. 1 is a graph showing the results of X-ray diffraction (XRD) analysis of two kinds of zinc ferrite catalysts used in Example 1 of the present invention
  • FIG. 2 is a graph showing the results of X-ray diffraction (XRD) analysis of three kinds of zinc ferrite catalysts used in Example 2 of the present invention
  • FIG. 3 is a graph showing the results of X-ray diffraction (XRD) analysis of two kinds of zinc ferrite catalysts used in Comparative Example.
  • FIG. 4 is a graph showing the change in the oxidative dehydrogenation reaction activity of C4 raffinate-3 to the pH of a buffer solution at the time of the coprecipitation of seven kinds of zinc ferrite catalysts used in Experimental Example 2 of the present invention. [Best Mode]
  • the present invention provides a method of preparing a zinc ferrite catalyst for producing 1,3-butadiene, in which a single phase zinc ferrite catalyst for use in the oxidative dehydrogenation reaction of n-butene is prepared using a buffer solution having fixed pH through a coprecipitation process without additionally controlling the pH of a precipitation solution, and provides a method of producing 1,3-butadiene through the oxidative dehydrogenation reaction of n-butene using the zinc ferrite catalyst. According to the present invention, even when a C4 mixture including n-butane is used as a reactant, 1,3-butadiene can be produced in high yield.
  • the catalyst of the present invention used to produce 1,3-butadiene through the oxidative dehydrogenation reaction of n-butene is a single phase zinc ferrite catalyst. Since the properties of metal cations and oxygen in a lattice are changed depending on the crystal structure of a catalyst, the activity of the catalyst can be changed by controlling the preparation conditions of the catalyst. Therefore, the present inventors developed methods of preparing a catalyst while changing the pH of a coprecipitation solution during a process of coprecipitating zinc ferrite. In these methods, a buffer solution was used in order to more efficiently control the pH of a coprecipitation solution, thereby preparing a zinc ferrite catalyst exhibiting high activity in the oxidative dehydrogenation reaction of n-butene.
  • All commonly used precursors can be used as a zinc precursor and an iron precursor for preparing the zinc ferrite catalyst.
  • chloride precursors or nitrate precursors may be used.
  • zinc chloride is used as the zinc precursor
  • iron chloride is used as the iron precursor.
  • the zinc precursor and iron precursor are quantitated such that the ratio of iron/zinc is
  • a buffer solution having a constant pH is prepared or provided.
  • the precursor solution is injected into the buffer solution using a syringe pump, zinc ferrite starts to be coprecipitated.
  • the precursor solution must be injected into a large amount of the buffer solution such that the pH of the buffer solution is not changed by the injection of the precursor solution.
  • the mixed solution is stirred for 2 ⁇ 12 hours, preferably 6 - 12, such that zinc ferrite is sufficiently coprecipitated, so as to obtain a coprecipitation solution.
  • the coprecipitation solution is sufficiently phase-separated such that the solid material dispersed in the coprecipitation solution is precipitated, and is then filtered using a vacuum filter to obtain a solid sample.
  • the solid sample is dried at a temperature of 70 ⁇ 200 ° C, preferably 120 ⁇ 180 ° C, for 12 - 16 hours, and is then heat-treated in an electric furnace at a temperature of 350 - 800 ° C, preferably 500 - 700 ° C , for 3 - 6 hours to prepare a pure single phase zinc ferrite catalyst.
  • the zinc ferrite catalyst serves to convert n-butene into 1,3 -butadiene and water through an oxidative dehydrogenation reaction by detaching hydrogen from n-butene through the interaction between the iron ions and oxygen ions in a catalyst lattice and the gaseous oxygen adsorbed on the surface of the catalyst and then additionally detaching hydrogen therefrom through the oxidation-reduction reaction of the gaseous oxygen and iron ions. Therefore, the properties of the iron and oxygen ions in the catalyst lattice and the characteristics of the surface of the catalyst greatly influence the determination of the activity of the catalyst in the oxidative dehydrogenation reaction of n- butene. Accordingly, the zinc ferrite catalysts prepared using precipitation solutions having various pH values exhibit different activities from each other.
  • the zinc ferrite catalyst for producing 1,3 -butadiene according to the present invention was prepared using precipitation solution having a pH of 6 ⁇ 12.
  • the zinc ferrite catalyst be prepared using precipitation solution having a pH of 6 ⁇ 10 (refer to FIG. 4).
  • the present invention provides a method of producing 1,3-butadiene through an oxidative dehydrogenation reaction on the zinc ferrite catalyst prepared using the buffer solution by using a C4 mixture or C4 raffinate-3 as a supply source of n-butene without performing a process of removing n-butane therefrom.
  • the oxidative dehydrogenation reaction is conducted by fixing catalyst powder on a straight pyrex reactor for catalytic reaction, installing the reactor in an electric furnace to maintain the temperature of a catalyst layer constant, and then continuously passing a reactant through the catalyst layer in the reactor.
  • the reaction temperature for performing the oxidative dehydrogenation reaction may be 300 - 600 0 C, preferably 350 ⁇ 500 ° C, and more preferably 420 0 C.
  • the amount of the reactant passing through the catalyst layer in the reactor is set such that gas hourly space velocity is 50 ⁇ 500Oh "1 , preferably 100 ⁇ 100Oh "1 , and more preferably 300 ⁇ 60Oh "1 .
  • the reactant is a mixed gas of a C4 mixture, air and steam, and the mixing ratio thereof is set such that the ratio of n-butene: air: steam is 1 : 0.5-10 : 1 —50, and preferably 1 : 3 ⁇ 4 : 10-30, based on n-butene.
  • the volume ratio of the mixed gas is more than or less than the above range, a desired yield of butadiene cannot be obtained, and problems with safety may occur due to a rapid exothe ⁇ nic reaction at the time of operation of the reactor.
  • n-butene (C4 mixture or C4 raffinate-3) and oxygen are supplied into a reactor, and the amount thereof is controlled using a mass flow controller.
  • steam is additionally supplied into the reactor. Specifically, steam is supplied into the reactor by injecting liquid water into the reactor using a syringe pump and simultaneously vaporizing the liquid water while maintaining the temperature of a water inlet at 150 - 300 ° C, and preferably 180 - 250 ° C . Further, steam is injected into the reactor, is completely mixed with other reactants (C4 mixture and air), and then passes through a catalyst layer, before it is introduced into an electric furnace.
  • the C4 mixture which is a reactant used in the present invention, includes 0.5 ⁇ 50 wt% of n-butane, 40 ⁇ 99 wt% of n-butene, and 0.5 - 10 wt% of other C4 compounds.
  • the C4 compounds include i-butane, cyclobutane, methyl cyclopropane, i-butene, and the like.
  • the zinc ferrite catalyst of the present invention When the zinc ferrite catalyst of the present invention is used, high catalytic activity and high 1,3-butadiene yield can be obtained even when a cheap C4 mixture or C4 raffinate-3 including a large amount of n-butane which is known to inhibit the oxidative dehydrogenation reaction of n-butene is directly used as a supply source of n-butene which is a reactant. Further, the present invention is a direct catalyst synthesis technology, rather than a subsidiary technology using a conventional substitution or catalyst treatment process, and has excellent reproducibility due to a simple catalyst composition and a simple synthesis mechanism.
  • the zinc ferrite catalyst of the present invention is advantageous in that, when it is used, 1,3-butadiene can be produced in high yield from a cheap C4 mixture or C4 raffinate-3 including impurities. [Mode for Invention]
  • Zinc chloride (ZnCl 2 ) was used as a zinc precursor, and iron chloride hexahydrate (FeCl 3 6H 2 O) was used as an iron precursor. Both the zinc precursor and the iron precursor are easily dissolved in distilled water. The respective precursors were quantitated such that the ratio of Fe/Zn is 2, mixed with each other, and then dissolved in distilled water to form a mixed solution. In this case, in order to form a sample having a uniform composition, the mixed solution was stirred using a magnetic stirrer for about 2 hours.
  • buffer solution for preparing a zinc ferrite catalyst in order to coprecipitate zinc ferrite, a buffer solution, the pH of which can be maintained constant, was used as a coprecipitation medium.
  • the buffer solution for preparing a zinc ferrite catalyst is directly prepared, or a commonly-used buffer solution was used as the buffer solution for preparing a zinc ferrite catalyst.
  • All buffer solutions can be used as the buffer solution of the present invention as long as they have constant pH values and do not form precipitates other than zinc ferrite.
  • a buffer solution in which hydrochloric acid is mixed with an aqueous sodium tetraborate solution was prepared. Specifically, 57.2 g (0.15 mol) of sodium tetraborate decahydrate was dissolved in distilled water to form 1 L of an aqueous sodium tetraborate solution having a concentration of
  • hydrochloric acid was added to the aqueous sodium tetraborate solution to form a mixed solution having a pH of 6 or 7. Subsequently, the mixed solution was stirred for about 2 hours to obtain a uniform buffer solution.
  • a buffer solution in which an aqueous sodium hydrogen carbonate solution is mixed with an aqueous sodium hydroxide solution was prepared. Specifically, 21.O g (0.25 mol) of sodium hydrogen carbonate was dissolved in distilled water to form 0.5L of an aqueous sodium hydrogen carbonate solution having a concentration of 0.5 M. Then, an aqueous sodium hydroxide solution was added to the aqueous sodium hydrogen carbonate solution to form a mixed solution having a pH of 1 1 or 12. Subsequently, the mixed solution was stirred for about 2 hours to obtain a uniform buffer solution.
  • a zinc ferrite catalyst In order to prepare a zinc ferrite catalyst, 1.42 g of zinc chloride and 5.61 g of iron chloride hexahydrate were dissolved in distilled water (250 mL), mixed with each other, and then stirred to form a precursor solution in which a zinc precursor and an iron precursor are completely dissolved in distilled water. Subsequently, the precursor solution was dropped into the above buffer solution having a pH of 6 ⁇ 12 to form a mixed solution, and simultaneously zinc ferrite was coprecipitated. The mixed solution was sufficiently stirred at room temperature for 12 hours using a magnetic stirrer, and was then left at room temperature for 12 hours for the purpose of phase separation.
  • the mixed solution in which zinc ferrite is coprecipitated was filtered using a vacuum filter to obtain a solid sample, and then the solid sample was dried at a temperature of 175 ° C for 16 hours. Subsequently, the dried solid sample was heat-treated in an electric furnace for 6 hours under an air atmosphere while the temperature of the electric furnace was maintained at 650 ° C, thereby preparing zinc ferrite catalysts.
  • the phases of the prepared zinc ferrite catalysts were observed through X-ray diffraction (XRD) analysis, and the results thereof are shown in FIGS. 1 to 3. From FIG.
  • the oxidative dehydrogenation reaction of n-butene was performed using the zinc ferrite catalyst prepared in Preparation Example under the following experimental conditions.
  • a C4 mixture was used as a reactant for the oxidative dehydrogenation reaction of n-butene, and the composition thereof is given in Table 1.
  • the C4 mixture was introduced into a reactor together with air and steam, and a straight pyrex fixed-
  • the constitution ratio of the reactant was set based on the amount of n-butene in the C4 mixture. That is, the volume ratio of n-butene: air: steam was set to a ratio of 1 : 3.75: 15, and, in this case, the volume ratio of n-butene: oxygen: steam was set to a ratio of 1 : 0.75: 15. Steam, which was formed by vaporizing liquid water at a temperature of 200 ° C, was mixed with a C4 mixture and air, and was then introduced into the reactor. The amount of the C4 mixture and the amount of air were controlled by a mass flow controller, and the amount of steam was controlled by controlling the flow rate of liquid water using a syringe pump.
  • the feed rate of the reactant was set such that gas hourly space velocity (GHSV) was 475 h "1 based on n-butene in the C4 mixture, and the reaction temperature was maintained such that the temperature of the catalyst layer of the fixed-bed reactor was 420 ° C .
  • gas chromatography was used in order to separate and analyze the reaction products.
  • Preparation Example were observed through X-ray diffraction (XRD) analysis. As a result, it was found that all of the catalysts have a single phase of zinc ferrite (refer to FIG. 2).
  • the oxidative dehydrogenation reaction of a C4 mixture was performed using three kinds of catalysts prepared using a buffer solution having a pH of 8 to 10, and the results thereof are given in Table 3. From Table 3, it can be seen that all of the three kinds of catalysts exhibit a high n-butene conversion ratio of 78% or more, a high 1,3 -butadiene selectivity of 92% or more and a high 1,3-butadiene of 72% or more. Therefore, it is preferred that a buffer solution having a pH of 8 to 10 be used in order to prepare a high-efficiency zinc ferrite catalyst according to the present invention.
  • the phases of the catalysts prepared using a sodium hydrogen carbonate-based buffer solution having a pH of 11 and 12 in Preparation Example were observed through X-ray diffraction (XRD) analysis. As a result, it was found that the catalysts have a single phase of zinc ferrite (refer to FIG. 3).
  • the oxidative dehydrogenation reaction of a C4 mixture was performed using the two kinds of catalysts prepared using a sodium hydrogen carbonate-based buffer solution having a pH of 1 1 and 12, and the results thereof are given in Table 4. From Table 4, it was found that, although the catalysts include a single phase zinc ferrite, the catalysts coprecipitated under a strong basic atmosphere exhibit very low catalytic activity.

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Abstract

Cette invention concerne un procédé permettant de préparer un catalyseur à base de ferrite de zinc au moyen d'une solution tampon et un procédé permettant de produire 1,3-butadiène au moyen du catalyseur à base de ferrite de zinc. Plus particulièrement, cette invention concerne un procédé permettant de préparer un catalyseur à base de ferrite de zinc directement au moyen d'une solution tampon en tant que milieu de coprécipitation sans ajuster le pH d'une solution de coprécipitation par adjonction supplémentaire d'acides et de bases dans la solution de coprécipitation. Cette invention concerne également un procédé permettant de produire du 1,3-butadiène au moyen du catalyseur à base de ferrite de zinc grâce à la réaction de déshydrogénation par oxydation d'un mélange C4 contenant n-butène et n-butane.
PCT/KR2008/005095 2007-10-02 2008-08-29 Procédé permettant de préparer des catalyseurs à base de ferrite de zinc au moyen d'une solution tampon et procédé permettant de préparer du 1,3-butadiène au moyen de ces catalyseurs Ceased WO2009045002A1 (fr)

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KR1020070099352A KR100950373B1 (ko) 2007-10-02 2007-10-02 완충 용액을 이용하는 아연 페라이트 촉매의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법
KR10-2007-0099352 2007-10-02

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WO2012030891A1 (fr) * 2010-09-02 2012-03-08 Saudi Basic Industries Corporation Catalyseur modifié de ferrite de zinc, procédé de préparation et utilisation de ce dernier
WO2014128718A3 (fr) * 2013-02-08 2014-12-24 Reliance Industries Limited Procédé de préparation d'un diène conjugué
WO2015173740A3 (fr) * 2014-05-13 2016-02-04 Reliance Industries Limited Procédé de production de diène conjugué à partir d'un flux de c4 mélangé
CN107614106A (zh) * 2016-03-25 2018-01-19 株式会社Lg化学 氧化脱氢用催化剂及其制备方法
RU2656104C2 (ru) * 2012-09-05 2018-05-31 Чайна Петролеум Энд Кемикл Корпорейшн Катализатор, предназначенный для окислительного дегидрирования бутена с получением бутадиена, и способ его получения
EP3308855A4 (fr) * 2016-03-18 2018-07-11 LG Chem, Ltd. Procédé de préparation de catalyseur pour déshydrogénation oxydative
EP3272417A4 (fr) * 2016-03-24 2019-01-09 LG Chem, Ltd. Catalyseur pour réaction de déshydrogénation oxydative et procédé de préparation de celui-ci
JP2019520204A (ja) * 2017-05-04 2019-07-18 エルジー・ケム・リミテッド 酸化的脱水素化反応用触媒の製造方法及びその触媒を用いた酸化的脱水素化方法
US10456775B2 (en) * 2016-03-28 2019-10-29 Lg Chem, Ltd. Method of preparing zinc ferrite catalyst
US20200001279A1 (en) * 2017-12-26 2020-01-02 Lg Chem, Ltd. Method for manufacturing zinc ferrite catalyst and zinc ferrite catalyst manufactured thereby
EP3671206A4 (fr) * 2017-08-18 2020-07-29 LG Chem, Ltd. Procédé d'analyse quantitative de chlore résiduel dans de la ferrite de zinc
US11865522B2 (en) 2019-09-27 2024-01-09 Lg Chem, Ltd. Method for preparing zinc ferrite-based catalyst and zinc ferrite-based catalyst prepared thereby

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KR101340620B1 (ko) * 2013-05-14 2013-12-31 금호석유화학 주식회사 허니컴 구조의 페라이트 금속산화물 촉매 성형체와 그의 제조방법 및 이를 이용한 1,3-부타디엔 제조방법
KR101340621B1 (ko) * 2013-05-14 2013-12-11 금호석유화학 주식회사 분무 열분해 방법을 이용한 페라이트 금속산화물 촉매와 그의 제조방법 및 이를 이용한 1,3-부타디엔 제조방법
KR101701973B1 (ko) * 2015-06-05 2017-02-03 금호석유화학 주식회사 페라이트 금속 산화물 촉매의 제조방법
KR102017207B1 (ko) 2015-12-09 2019-09-02 주식회사 엘지화학 산화적 탈수소화 반응용 촉매 및 이의 제조방법
KR102044058B1 (ko) * 2016-06-24 2019-11-12 주식회사 엘지화학 부타디엔의 제조방법
KR102229193B1 (ko) * 2017-05-04 2021-03-17 주식회사 엘지화학 산화적 탈수소화 반응용 촉매, 이의 제조방법 및 부타디엔 제조방법
WO2018203615A1 (fr) * 2017-05-04 2018-11-08 (주) 엘지화학 Procédé de préparation de catalyseur pour réaction de déshydrogénation oxydative et procédé de déshydrogénation oxydative faisant appel audit catalyseur

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US8551443B2 (en) 2010-09-02 2013-10-08 Saudi Basic Industries Corporation Modified zinc ferrite catalyst and method of preparation and use
WO2012030891A1 (fr) * 2010-09-02 2012-03-08 Saudi Basic Industries Corporation Catalyseur modifié de ferrite de zinc, procédé de préparation et utilisation de ce dernier
RU2656104C2 (ru) * 2012-09-05 2018-05-31 Чайна Петролеум Энд Кемикл Корпорейшн Катализатор, предназначенный для окислительного дегидрирования бутена с получением бутадиена, и способ его получения
WO2014128718A3 (fr) * 2013-02-08 2014-12-24 Reliance Industries Limited Procédé de préparation d'un diène conjugué
WO2015173740A3 (fr) * 2014-05-13 2016-02-04 Reliance Industries Limited Procédé de production de diène conjugué à partir d'un flux de c4 mélangé
EP3308855A4 (fr) * 2016-03-18 2018-07-11 LG Chem, Ltd. Procédé de préparation de catalyseur pour déshydrogénation oxydative
US10926246B2 (en) 2016-03-18 2021-02-23 Lg Chem, Ltd. Method of preparing catalyst for oxidative dehydrogenation
US10543478B2 (en) 2016-03-24 2020-01-28 Lg Chem, Ltd. Catalyst for oxidative dehydrogenation and method of preparing the same
EP3272417A4 (fr) * 2016-03-24 2019-01-09 LG Chem, Ltd. Catalyseur pour réaction de déshydrogénation oxydative et procédé de préparation de celui-ci
CN107614106A (zh) * 2016-03-25 2018-01-19 株式会社Lg化学 氧化脱氢用催化剂及其制备方法
EP3292910A4 (fr) * 2016-03-25 2019-04-03 LG Chem, Ltd. Catalyseur servant à une réaction de déshydrogénation oxydative, et son procédé de préparation
US10486150B2 (en) 2016-03-25 2019-11-26 Lg Chem, Ltd. Catalyst for oxidative dehydrogenation and method of preparing the same
US10456775B2 (en) * 2016-03-28 2019-10-29 Lg Chem, Ltd. Method of preparing zinc ferrite catalyst
JP2019520204A (ja) * 2017-05-04 2019-07-18 エルジー・ケム・リミテッド 酸化的脱水素化反応用触媒の製造方法及びその触媒を用いた酸化的脱水素化方法
US11247195B2 (en) 2017-05-04 2022-02-15 Lg Chem, Ltd. Method of preparing catalyst for oxidative dehydrogenation and method of performing oxidative dehydrogenation using catalyst
EP3671206A4 (fr) * 2017-08-18 2020-07-29 LG Chem, Ltd. Procédé d'analyse quantitative de chlore résiduel dans de la ferrite de zinc
US11249060B2 (en) 2017-08-18 2022-02-15 Lg Chem, Ltd. Method for quantitatively analyzing residual Cl in zinc ferrite
US20200001279A1 (en) * 2017-12-26 2020-01-02 Lg Chem, Ltd. Method for manufacturing zinc ferrite catalyst and zinc ferrite catalyst manufactured thereby
EP3552701A4 (fr) * 2017-12-26 2020-03-18 Lg Chem, Ltd. Procédé de fabrication d'un catalyseur de ferrite de zinc et catalyseur de ferrite de zinc ainsi fabriqué
US11040335B2 (en) 2017-12-26 2021-06-22 Lg Chem, Ltd. Method for manufacturing zinc ferrite catalyst and zinc ferrite catalyst manufactured thereby
US11865522B2 (en) 2019-09-27 2024-01-09 Lg Chem, Ltd. Method for preparing zinc ferrite-based catalyst and zinc ferrite-based catalyst prepared thereby

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