KR101248697B1 - Method of Producing Magnesia-zirconia Carrier for Catalyst for Oxidative Dehydrogenation of n-Butane, Method of Producing Magnesia-zirconia Carrier-Supported Magnesium Orthovanadate Catalyst, and Method of Producing n-Butene and 1,3-Butadiene Using Said Catalyst - Google Patents

Abstract

The present invention provides a method for preparing a magnesia-zirconia composite carrier for oxidative dehydrogenation reaction catalyst of normal-butane, a method for preparing a magnesium orthovanadate catalyst supported on a magnesia-zirconia composite carrier prepared therefrom, and a normal using the catalyst. It relates to a method for producing butene and 1,3-butadiene.

Description

Method for preparing magnesia-zirconia composite carrier for oxidative dehydrogenation reaction catalyst of normal-butane, method for preparing magnesium orthovanadate catalyst supported on magnesia-zirconia composite carrier prepared therefrom and normal-butene Method of Producing Magnesia-zirconia Carrier for Catalyst for Oxidative Dehydrogenation of n-Butane, Method of Producing Magnesia-zirconia Carrier-Supported Magnesium Orthovanadate Catalyst, and Method of Producing n-Butene and 1,3 -Butadiene Using Said Catalyst}

The present invention provides a method for preparing a magnesia-zirconia composite carrier for oxidative dehydrogenation reaction catalyst of normal-butane, a method for preparing a magnesium orthovanadate catalyst supported on a magnesia-zirconia composite carrier prepared therefrom, and a normal using the catalyst. It relates to a method for producing butene and 1,3-butadiene.

Recently, as olefin prices have soared in the petrochemical market, the supply of light olefins, which is a raw material for various petrochemical products, has become a concern of the market. Normal-butene and 1,3-butadiene, which are raw materials for various synthetic rubber and copolymer products, are also one of the light olefins, which have recently been increasing in demand and value, mainly in China. Direct dehydrogenation of butane or normal-butene or oxidative dehydrogenation of normal-butane or normal-butene. Among them, about 90% or more of the normal-butene and 1,3-butadiene supplied to the market is supplied by the naphtha cracking process, and thus the operation of the naphtha cracking process on the market is very significant. However, the naphtha cracking process is not a sole process for producing normal-butene and 1,3-butadiene due to the nature of the process for the production of basic fractions such as ethylene and propylene, and thus, normal-butene and 1,3-butadiene Naphtha crackers cannot be expanded or expanded in order to expand production, and even if naphtha crackers are added, other basic oils other than normal-butene and 1,3-butadiene are produced in surplus. In addition, the recent trend in the establishment and operation of naphtha cracking process is in the direction of high yield as the demand for ethylene and propylene is greatly increased, so that the yield for C ₄ fraction is low and instead of ethylene and propylene, It is changing to the process which uses light hydrocarbons, such as ethane and propane, which have a high yield with respect to other basic fractions as a raw material. While there have continued to rise and the rate of the C ₄ naphtha to obtain the oil fraction raw material to thereby relatively naphtha cracking due to process the ratio it is so reduced, due to various causes, of the C ₄ mixture through a naphtha cracking process, in particular It is becoming increasingly difficult to obtain normal-butenes and 1,3-butadiene.

As mentioned above, the naphtha cracking process accounts for most of the supply of normal-butene and 1,3-butadiene, but for many reasons, the supply-demand imbalance caused by the recent increase in demand for normal-butene and 1,3-butadiene can be resolved. Since it cannot be an effective alternative, the dehydrogenation reaction of removing hydrogen from normal-butane or normal-butene to obtain normal-butene and 1,3-butadiene is drawing attention as a process that can cope with recent market changes quickly. .

However, over the past two decades, dehydrogenation through normal-butene, which is relatively easy to dehydrogenation among normal-butane and normal-butene, has been actively studied, and many research results have been published [H.H. Kung, M.C. Kung, Adv. Catal., Vol. 33, 159 (1985); J.A. Toledo, P. Bosch, M.A. Valenzuela, A. Montoya, N. Nava, J. Mol. Catal. A, vol. 125, 53 (1997); H. Lee, J.C. Jung, H. Kim, Y.-M. Chung, T.J. Kim, S.J. Lee, S.-H. Oh, Y.S. Kim, I.K. Song, Catal. Lett., Vol. 131, p. 344 (2009); H. Lee, J.C. Jung, I.K. Song, Catal. Lett., Vol. 133, p. 321 (2009); W. Ueda, K. Asakawa, C.-L. Chen, Y. Moro-oka, T. Ikawa, J. Catal., Vol. 101, 360 (1986); R.K. Grasselli, Handbook of Heterogeneous Catalysis, 5, 2302 (1997); J.C. Jung, H. Lee, H. Kim, Y.-M. Chung, T.J. Kim, S.J. Lee, S.-H. Oh, Y.S. Kim, I.K. Song, Catal. Lett., Vol. 124, 262 (2008); J.C. Jung, H. Lee, D. R. Park, J.G. Seo, I.K. Song, Catal. Lett., Vol. 131, p. 401 (2009)], and also recently, normal-butene prices have been soaring due to the surge in demand in China, and ultimately in the petrochemical industry, the oxidative dehydrogenation reaction of normal-butane is now normal. -It is considered as a countermeasure to solve the butene and 1,3-butadiene supply and demand imbalance, and the related research is being actively conducted [N. Kijima, M. Toba, Y. Yoshimura, Catal. Lett., Vol. 127, 63 (2009); I.C. Marcu, I. Sandulescu, J.M.M. Millet, Appl. Catal. A, Vol. 227, p. 309 (2002); L.M. Madeira, J.M. Herrmann, F.G. Freire, M.F. Portela, F.J. Maldonado, Appl. Catal. A, Vol. 158, 243 (1997); A.A. Lemonidou, G.J. Tjatjopoulos, I.A. Vasalos, Catal. Today, Vol. 45, 65 (1998)].

The dehydrogenation of normal-butane includes direct dehydrogenation and oxidative dehydrogenation, which is a highly endothermic reaction because it is necessary to remove hydrogen directly from normal-butane. It is disadvantageous, and high temperature reaction conditions are required, which consumes a lot of energy. In addition, a noble metal catalyst such as platinum or palladium is used to perform a direct dehydrogenation reaction. In the case of such a noble metal catalyst, the life of the noble metal catalyst is very short, and a regeneration process has to be performed. It is not suitable as a commercialization process for butadiene production [A. Wu, C.A. Frake, US Pat. No. 6,433,241 B2 (2002); A. Wu, C.A. Frake, US Patent No. 6,187,984 (2001)]. On the other hand, oxidative dehydrogenation of normal-butane is different from direct dehydrogenation, in which normal-butane reacts with oxygen to produce normal-butene and water, and normal-butene reacts with 1,3-butadiene. In the reaction that turns into water, as the endothermic reaction is converted to exothermic reaction as oxygen is used to generate water, not only is thermodynamically advantageous, but also the rapid temperature of the catalyst layer because the water generated after the reaction can suppress the heat generated by the catalytic reaction. Changes can be prevented. Therefore, unlike the naphtha cracking process, the oxidative dehydrogenation process of normal-butane produces normal-butene and 1,3-butadiene by a single process, and can be operated under favorable process conditions than the direct dehydrogenation process. If a catalytic process for producing normal-butene and 1,3-butadiene is developed, this process can be an effective alternative to the production of normal-butene and 1,3-butadiene by energy-saving single process.

As described above, in the production of normal-butene and 1,3-butadiene, the oxidative dehydrogenation of normal-butane reacts with normal-butane and oxygen to produce normal-butene and water, and from normal-butene and oxygen The same process occurs once more, producing 1,3-butadiene and water. As mentioned above, this reaction is thermodynamically advantageous compared to the normal dehydrogenation of normal-butane as a compatibilization process, so that a higher yield of normal-butene and 1,3-butadiene can be obtained even under mild reaction conditions. Although it has many advantages, many side reactions such as highly oxidative reactions that generate carbon monoxide or carbon dioxide are expected because oxygen is used as a reactant in the present reaction.

Therefore, the development of a catalyst capable of increasing the selectivity of normal-butene and 1,3-butadiene by suppressing side reactions such as complete oxidation while maximizing the conversion of normal-butane is essential in the process of oxidative dehydrogenation of normal-butane. In the most important core technology. The mechanism of the reaction of oxidative dehydrogenation of normal-butane is not yet known precisely, but the first step is to remove the CH bond from normal-butane by the action of a solid acid-intermediate, while simultaneously reducing the oxidation and reduction reactions and lattice of the catalyst itself. Loss of oxygen is known to occur, and catalysts in the form of complex oxides containing transition metal ions, which can have various oxidation states, are essential for oxidative dehydrogenation reactions [HH Kung, Ind. Eng. Chem. Prod. Res. Dev., 25, 171 (1986)].

To date, catalysts known to be effective for preparing normal-butene and 1,3-butadiene by oxidative dehydrogenation of normal-butane are magnesium orthovanadate series catalysts [M.A. Chaar, D. Partel, H. H. Kung, J. Catal., 105, 483 (1987); M.A. Chaar, D. Partel, H. H. Kung, J. Catal., Vol. 109, 463 (1988); O.S. Owen, H. H. Kung, J. Mol. Catal., Vol. 79, p. 265 (1993); A.A. Lemonidou, G.J. Tjatjopoulos, I.A. Vasalos, Catal. Today, 45, 65 (1998); Song In-gyu, Lee Ho-won, Yoo-Sik Cho, Young-Jin Cho, Jin-Suk Lee, Ho-Sik Jang, Republic of Korea Patent Application 10-2011-0021037 (2011)], Vanadium oxide-based catalyst [A.F. Dickason, US Pat. No. 3,914,332 (1975); M.E. Harlin, V.M. Niemi, A.O.I. Krause, J. Catal. 195, p. 67 (2000); V.M. Murgia, E.M.F. Torres, J.C. Gottifredi, E.L. Sham, Appl. Catal. A, Vol. 312, p. 134 (2006)], pyrophosphate-based catalysts [I.C. Marcu, I. Sandulescu, J.M.M. Millet, Appl. Catal. A, Vol. 227, p. 309 (2002); F. Urlan, I.C. Marcu, I. Sandulescu, Catal. Commun., Vol. 9, p. 2403 (2008)], ferrite-based catalysts [H. Armendariz, J.A. Toledo, G. Aguilar-Rios, M.A. Valenzuela, P. Salas, A. Cabral, H. Jimenez, I. Schifter, J. Mol. Catal., Vol. 92, p. 325 (1994); L. Bajars, L.J. Croce, US Pat. No. 3,303,234 (1967).

A common feature of these complex oxide catalysts is that they comprise a transition metal, as described above, since electron transfer between the catalyst and normal-butane must be possible through oxidation-reduction of the catalyst [H.H. Kung, Ind. Eng. Chem. Prod. Res. Dev., 25, 171 (1986)]. The catalysts may perform an oxidative dehydrogenation reaction of normal-butane by including an oxide-reducing metal such as vanadium, iron, nickel, titanium, and the like. In particular, a magnesium orthovanadate-based catalyst including vanadium The activity of these compounds is known to be high, and the oxidation-reduction ability of vanadium metal may be judged to be suitable for the oxidative dehydrogenation of normal-butane. Chaar, D. Partel, H. H. Kung, J. Catal., 105, 483 (1987); M.A. Chaar, D. Partel, H. H. Kung, J. Catal., Vol. 109, 463 (1988)].

The above-mentioned magnesium orthovanadate-based catalyst has a chemical formula of Mg ₃ (VO ₄ ) ₂ , and has a tetragonal crystal form, which is combined with magnesia in the oxidative dehydrogenation of normal-butane, and thus the reaction conditions. According to the present invention, the cubic crystalline structure is reduced to Mg ₂ VO ₄ in the form of vanadium tetraoxide, and reduced to MgV ₂ O ₄ and oxygen in the form of vanadium trioxide [N. Kijima, M. Toba, Y. Yoshimura, Catal. Lett., Vol. 127, 63 (2009)], this reduction process takes place by accepting electrons from the breakdown of CH bonds from normal-butane. Reduction of vanadium ions, which are the central metals, from the oxidized state to the trioxide state is essential for the oxidative dehydrogenation of normal-butane. The magnesium orthovanadate-based catalyst is a normal through the oxidation number change of vanadium. -Can be used as a catalyst in the oxidative dehydrogenation reaction of performing normal-butene and 1,3-butadiene from the normal-butane by performing an oxidation-reduction reaction with butane [N. Kijima, M. Toba, Y. Yoshimura, Catal. Lett., Vol. 127, 63 (2009)].

In general, magnesium orthovanadate catalyst is prepared in a form in which the active phase of Mg ₃ (VO ₄ ) ₂ is supported on a separate metal oxide. In the case of unsupported magnesium orthovanadate catalyst, the supported magnesium orthovanadate is supported. It is reported to be less active.

The results of oxidative dehydrogenation of normal-butane using magnesium orthovanadate catalysts not supported in the prior patents and literature have been reported. Specifically, the reactant injection ratio is normal-butane: oxygen: helium = 4: It was reported that the reaction at 540 ° C. at 8:88 gave 11.5% normal-butane conversion and 6.7% dehydrogenation product yield [OS. Owen, H. H. Kung, J. Mol. Catal., Vol. 79, p. 265 (1993)], Normal-Butane Oxidation at 540 ° C. with Unsupported Magnesium Orthovanadate Catalyst Under Reaction Injection Ratio Normal-Butane: Oxygen: Helium = 5: 10: 85 It was reported that red dehydrogenation reaction yielded a yield of 5.7% dehydrogenation reaction product [AA Lemonidou, G.J. Tjatjopoulos, I.A. Vasalos, Catal. Today, Vol. 45, 65 (1998)]. Magnesium orthovanadate catalysts can enhance their activity when supported [A.A. Lemonidou, G.J. Tjatjopoulos, I.A. Vasalos, Catal. Today, Vol. 45, 65 (1998)], in particular, magnesium orthovanadate catalysts supported on magnesia obtained by supporting vanadium in an excess of magnesia are generally reported, and magnesium orthovanadate catalysts supported on such magnesia are generally reported. Has been reported to exhibit good activity in the oxidative dehydrogenation of normal-butane [MA Chaar, D. Partel, H. H. Kung, J. Catal., Vol. 109, 463 (1988); O.S. Owen, H. H. Kung, J. Mol. Catal., Vol. 79, p. 265 (1993); A.A. Lemonidou, G.J. Tjatjopoulos, I.A. Vasalos, Catal. Today, Vol. 45, 65 (1998)]. Specifically, the magnesium orthovanadate catalyst supported on magnesia synthesized by mixing magnesium hydroxide in a mixed aqueous solution of ammonium vanadate and ammonia so that the ratio of magnesium and vanadium is 6: 1 was 600 ° C., and normal- in the reaction product. The oxidative dehydrogenation of normal-butane was carried out under a butane: oxygen: nitrogen ratio of 2: 1: 97, resulting in 30.4% normal-butane conversion, 70.6% dehydrogenation product selectivity, and 21.5%. It was reported that the yield of dehydrogenation reaction product was obtained [N. Kijima, M. Toba, Y. Yoshimura, Catal. Lett., Vol. 127, p. 63 (2009)], normal at 540 ° C. via magnesium orthovanadate catalyst supported on magnesia under a reaction ratio of normal-butane: oxygen: helium = 5: 10: 85 It was reported that a butane oxidative dehydrogenation reaction yielded a yield of 22.8% [AA Lemonidou, G.J. Tjatjopoulos, I.A. Vasalos, Catal. Today, Vol. 45, 65 (1998)]. In addition, a magnesium orthovanadate catalyst supported on magnesia and a 35.4% normal-butane conversion rate and 18.1 at a higher oxygen ratio than those described above (normal-butane: oxygen: helium = 5: 20: 75) Experimental results with% dehydrogenation yield were also reported [JM Lopez Nieto, A. Dejoz, M.J. Vazquez, W. O'Leary, J. Cunnungham, Catal. Today, 40, 215 (1998)].

By adding the additive to the magnesium orthovanadate catalyst supported on magnesia, the activity of the normal-butane in the oxidative dehydrogenation reaction can be enhanced to obtain the dehydrogenation reaction products normal-butene and 1,3-butadiene in high yield. Literature on the application of magnesium orthovanadate catalysts has been reported [D. Bhattacharyya, S.K. Bej, M.S. Rao, Appl. Catal. A, Vol. 87, p. 29 (1992)], in this document a mixture of titanium oxide and chromium oxide on a magnesium orthovanadate catalyst supported on 25% by weight of magnesia, 570 ° C., normal-butane: oxygen: nitrogen ratio It was reported that under this condition 4: 8: 88, a normal-butane conversion of 54.0% and a yield of dehydrogenation reaction product of 33.8% were obtained.

In carrying out the oxidative dehydrogenation of normal-butane, when the magnesium orthovanadate catalyst supported on magnesia is used, the normal-butane-butane is a product of the oxidative dehydrogenation reaction of normal-butane. Butene and 1,3-butadiene can be obtained, but there are limitations to their commercial application. This is because the magnesium orthovanadate catalyst supported on magnesia is highly irreversible but the oxidation-reduction of the catalyst which has to be reversibly performed in the catalytic reaction process is partially irreversible [N. Kijima, M. Toba, Y. Yoshimura, Catal. Lett., Vol. 127, 63 (2009)], because the high activity of magnesium orthovanadate catalysts supported on magnesia is not maintained for a long time.

Accordingly, the inventors of the present invention have developed a low-cost and easy process without problems such as reduced activity over time of the magnesium orthovanadate catalyst supported on magnesia and low activity of other vanadium oxide catalysts. Magnesium orthovanadate supported by zirconia, which is capable of producing a catalyst but has a high activity of normal-butane in oxidative dehydrogenation reaction, and in particular, thermally and chemically stable without change in catalytic activity during the reaction. We have recently established a technique for preparing a catalyst and have recently developed a catalytic reaction process for producing normal-butene and 1,3-butadiene in a stable and high yield using the catalyst thus prepared [Song, In-Kyu, Ho-Won Lee, Yeon-Sik Cho, Young-Jin Cho] , Lee Jin-Seok, Jang Ho-Sik, Korea Patent Application 10-2011-0021037 (2011)].

In the above patent application, the present inventors prepare a zirconia carrier for the oxidative dehydrogenation reaction catalyst of normal-butane by gel-oxalate method, and prepare magnesium orthovanadate catalyst supported on zirconia by supporting magnesium and vanadium. In this way, a catalytic process capable of obtaining a stable and high probability of normal-butene and 1,3-butadiene through oxidative dehydrogenation of normal-butane was developed. However, in the above catalytic process, a magnesium orthovanadate catalyst supported on zirconia is used as a catalyst, which is capable of maintaining long-term activity compared to the magnesium orthovanadate catalyst supported on magnesia according to the prior art, and inactivated magnesium orthosorbate. There is an advantage in that a high activity can be obtained compared to the activity of the nadate catalyst, but there is a limit that the activity is lower than the initial activity of the magnesium orthovanadate catalyst supported on magnesia. Therefore, there is a need to develop a new catalyst that can maintain the activity of the catalyst without abandoning the initial activity of the magnesium orthovanadate catalyst supported on magnesia.

Accordingly, the inventors have continued to study the magnesium orthovanadate catalyst supported on magnesia as previously reported and previous patent application technology by the inventors In order to overcome the limitation of 2011-0021037 (2011), it is utilized as a carrier of magnesium orthovanadate catalyst, and when applied to the oxidative dehydrogenation reaction of normal-butane, there is no sign of deactivation of the catalyst. A method of preparing a magnesia-zirconia composite carrier for an oxidative dehydrogenation catalyst capable of obtaining higher activity than a magnesium orthovanadate catalyst supported on zirconia has been invented. In addition, while maintaining the stability of the catalyst to the oxidative dehydrogenation of the magnesium orthovanadate catalyst supported on the zirconia through a simple process of supporting the vanadium in the magnesia-zirconia composite carrier prepared according to the prior art The magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier, which can obtain the initial activity that does not fall significantly compared to the initial activity of the magnesium orthovanadate catalyst by using the same, was used as a reactant using normal-butane Through oxidative dehydrogenation, it was possible to prepare normal-butene and 1,3-butadiene in high yield, and based on this, the present invention was completed.

Accordingly, an object of the present invention is to provide a high activity without degrading the activity of magnesium orthovanadate, even when applied to the oxidative dehydrogenation reaction of normal-butane for supporting the active ingredient consisting of magnesium orthovanadate. It is to provide a method for producing a magnesia-zirconia composite carrier obtainable.

Another object of the present invention is to carry a magnesium orthovanadate active ingredient on a magnesia-zirconia composite carrier prepared by the method for preparing a carrier for the oxidative dehydrogenation reaction of normal-butane according to the present invention, magnesia It is to provide a method for preparing a magnesium orthovanadate catalyst supported on a zirconia composite carrier.

It is still another object of the present invention to use a catalyst supporting magnesium orthovanadate in a magnesia-zirconia composite carrier prepared by the above-described manufacturing method. Lee, Jin-Seok, Jang Ho-Sik, and Korea Patent Application 10-2011-0021037 (2011)], while maintaining the stability of the magnesium orthovanadate catalyst reaction process supported on zirconia, magnesium orthovanadate supported on magnesia The present invention provides a method for preparing normal-butene and 1,3-butadiene in high yield by performing an oxidative dehydrogenation reaction of normal-butane, which can obtain an initial activity which is not significantly inferior to a process using a catalyst.

In order to solve the above problems, the present invention provides a process for producing a magnesia-zirconia composite carrier for an oxidative dehydrogenation catalyst of n-butane, comprising the steps of:

(a) dissolving a zirconium precursor and oxalic acid in alcohol to prepare a zirconium alcohol solution and an oxalic acid alcohol solution, respectively;

(b) synthesizing zirconia by mixing the zirconium alcohol solution and the oxalic acid alcohol solution prepared in step (a);

(c) separating, drying and heat-treating zirconia as a solid component from the resultant solution obtained in step (b) to obtain zirconia for the preparation of the magnesia-zirconia composite carrier;

(d) impregnating an aqueous solution of magnesium salt in the zirconia obtained in step (c); And

(e) drying and heat-treating the resultant obtained in step (d) to obtain a magnesia-zirconia composite carrier for oxidative dehydrogenation reaction catalyst of normal-butane.

The zirconium precursor used in step (a) can be used as long as it is a commonly used precursor, which is generally selected from a chloride precursor, an oxynitrate precursor, and an oxychloride precursor of zirconium. Preference is given to using at least one kind, particularly preferably to zirconium chloride.

As the oxalic acid used in step (a), commercially available commercially available products can be used without limitation. For example, oxalic acid dihydrate is preferable.

The alcohol used in the step (a) can be used without limitation as long as it can dissolve the zirconium precursor and oxalic acid, alcohols such as ethanol, propanol, butanol, 2-butanol are preferable, and ethanol is particularly preferable.

In step (a), the zirconium precursor and the oxalic acid dissolved in the alcohol are preferably used in a molar ratio of 2 moles or more of oxalic acid with respect to 1 mole of zirconium, and the amount of oxalic acid required to convert all of the zirconium ions into zirconium oxalate is This is theoretically doubled. Therefore, oxalic acid can be used in more than twice the molar ratio of zirconium to convert the entire amount of zirconium ions into zirconium oxalate, but there are possibilities that unpredictable variables such as acidity of the solvent due to oxalic acid may occur. It is preferable to use in the molar ratio of 2-5.

There is no particular limitation on the method of mixing the zirconium alcohol solution and the oxalic acid alcohol solution in the step (b), so that the mixing of each solution is preferably mixed as slowly as possible so that the size of the zirconium oxalate particles can be evenly grown. It is preferable to keep the temperature of the stirring solution at room temperature. For example, the oxalic acid alcohol solution is put in a syringe and injected into a zirconium alcohol solution so as to be mixed as slowly as possible by precisely adjusting the speed with a syringe pump, so that the synthesis of zirconia is performed for 1 to 12 hours at room temperature, preferably 3 It is preferable to mix, stirring for 6 hours.

In the step (c), the solution stirred for a sufficient time in the step (b) is allowed to stand for a sufficient time to precipitate a solid component, and then subjected to phase separation, followed by filtration with alcohol to sufficiently remove chloride ions to obtain a solid sample. . For example, the solid component precipitated through a filter or centrifuge is separated from the alcohol solution to obtain a solid sample. The obtained solid sample is dried and the dried solid sample is heat treated to obtain pure zirconia.

Since the purpose of drying the solid sample is to remove the alcohol and water remaining after the separation process of obtaining the sample, generally set the temperature at which the alcohol can be evaporated as a lower limit, and further change by heat of the additional sample can be suppressed. The temperature which can be taken as an upper limit can also be made, and also drying time can also be limited within the time range in which alcohol is expected to be removed from a sample completely. For example, drying temperature is 50-200 degreeC, Preferably it is 70-120 degreeC, and drying time can be set to 3 to 24 hours, Preferably it is 6 to 12 hours.

The heat treatment of the dried solid sample is not only for synthesizing zirconium oxalate to zirconia, but also considering the reaction temperature of the oxidative dehydrogenation reaction of normal-butane, a catalyst supported on the prepared carrier may be used for the reaction. In order to suppress denaturation of the catalyst at the time, for example, put into an electric furnace and heat-treated for 1 to 12 hours, preferably 3 to 6 hours at a temperature of 350 to 800 ℃, preferably 500 to 700 ℃, heat treatment temperature Is less than 350 ° C. or the heat treatment time is less than 1 hour, the zirconium oxalate is not sufficiently synthesized into zirconia, which is undesirable. If the heat treatment temperature exceeds 800 ° C. or the heat treatment time exceeds 12 hours, the crystal phase of zirconia is deteriorated. This is not preferable because there is a possibility that it may not be suitably used as a carrier.

In the step (d), to form magnesia on the pure zirconia obtained by the method according to the step (c) to prepare the magnesia-zirconia composite carrier, as the magnesium salt used is a salt containing magnesium commonly used Any one can be used, but in order to minimize the effects of ions contained in the salt, magnesium salts in which anions are removed during the heat treatment after impregnation and drying are preferable. For example, magnesium nitrate is supported on zirconia. It is preferable to use as a magnesium salt to obtain the magnesia-zirconia composite carrier.

The amount of magnesium salt for obtaining the magnesia-zirconia composite carrier in step (d) may be determined without particular limitation, but one mole of vanadium to be supported on the magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier to be prepared finally Magnesium is preferably used at a molar ratio of 1.5 times or more, which is 1.5 times the molar ratio of magnesium to vanadium in terms of magnesium orthovanadate, theoretically at least 1.5 to form magnesium orthovanadate. Because you need a pear magnesium. More preferably, the amount of magnesium salt should be about 3 to 7 times for 1 mole of vanadium to be supported. The lower limit is that a magnesium orthovanadate catalyst is formed and the remaining magnesium must be present at an appropriate level of magnesia. May be present as a magnesia-zirconia composite carrier, and the upper limit is set in that if the amount of magnesium is too large, the component ratio of zirconia in the magnesia-zirconia composite carrier is too small to maintain the stability of the catalyst.

The component ratio of magnesia and zirconia forming the magnesia-zirconia composite carrier in step (d) is not particularly limited, but to prepare a carrier for magnesium orthovanadate catalyst which can stably maintain high initial activity for a long time. Preferably, the molar ratio of magnesia to zirconia is limited to 0.5 to 16: 1, preferably 0.5 to 4: 1.

In the step (d), the aqueous magnesium salt solution may be prepared by dissolving the magnesium salt in distilled water, in which the amount of water in the aqueous solution is sufficient to dissolve the magnesium salt, preferably impregnated with as little as possible.

In step (e), the resultant obtained in step (d) is dried, and the dried solid sample is heat-treated to obtain a magnesia-zirconia composite carrier for oxidative dehydrogenation reaction.

Since the purpose of drying in step (e) is to remove moisture remaining after impregnating zirconia with magnesium salt, the drying temperature and drying time can be defined according to general moisture drying conditions, for example, drying temperature. Is 50-200 degreeC, Preferably it is 70-120 degreeC, and drying time can be set as 3 to 24 hours, Preferably it is 6 to 12 hours.

In the step (e), the heat treatment is performed for 1 to 12 hours, preferably for 3 to 6 hours in a temperature range of, for example, 350 to 800 ° C, preferably 500 to 700 ° C. Is less than 350 ° C. or the heat treatment time is less than 1 hour, there is a possibility that the synthesis of magnesia may not be sufficient, and zirconia is denatured when the heat treatment temperature exceeds 800 ℃ or the heat treatment time is more than 12 hours This is because there is a fear that it is not preferable.

A process for producing a magnesium orthosubnadate catalyst supported on a magnesia-zirconia composite carrier according to the present invention using the above-prepared magnesia-zirconia composite carrier comprises the following steps:

(i) impregnating the magnesia-zirconia composite carrier produced by the above-mentioned method with an aqueous vanadium salt solution;

(ii) drying and heat-treating the resultant product obtained in the step (i), thereby preparing a magnesium orsorbanadate catalyst supported on the magnesia-zirconia composite carrier.

The vanadium salt used in the catalyst preparation method of the present invention can be any conventionally used vanadium salt without limitation. For example, it is preferable to use ammonium metavanadate, , But may further comprise other vanadium salts conventionally used for any purpose. However, when ammonium metavanadate is used as the vanadium salt, the ammonium ion is removed by impregnation, drying and heat treatment to reduce the influence of ions to the maximum, so that the vanadium salt is preferably used as the vanadium salt for carrying on the magnesia- Do.

The vanadium salt aqueous solution can be prepared by dissolving the vanadium salt in an aqueous solution of oxalic acid or by dissolving it in ammonia water. The amount of water in the aqueous solution is used only to the extent sufficient to dissolve each salt, It is desirable to use as few as possible. At this time, oxalic acid or ammonia water to help dissolve the vanadium salt can be used commercially available commercially available products without limitation, for example, oxalic acid dihydrate is preferable.

Since the purpose of drying in step (ii) is to remove moisture remaining after impregnating vanadium salt, the drying temperature and drying time may be defined according to general moisture drying conditions, for example, the drying temperature is 50 -200 degreeC, Preferably it is 70-120 degreeC, and drying time can be set as 3 to 24 hours, Preferably it is 6 to 12 hours.

In addition, the heat treatment in step (ii) is carried out for the purpose of dissolving the vanadium salt, removing oxalic acid for impregnation, and further synthesizing the vanadium salt supported on the magnesia-zirconia composite carrier as magnesium orthovanadate, It is preferably carried out for 1 to 12 hours, preferably for 3 to 6 hours in the temperature range of 350 to 800 ℃, preferably 500 to 700 ℃. This is not preferable because the synthesis of magnesium orthovanadate is not sufficient when the heat treatment temperature is less than 350 ° C. or when the heat treatment time is less than 1 hour, and when the heat treatment temperature exceeds 800 ° C. or when the heat treatment time exceeds 12 hours. It is not preferable because the magnesia-zirconia complex carrier may denature the crystal phase of zirconia.

The magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier of the present invention prepared as described above is a magnesium orthovanadate catalyst supported on magnesia according to the prior art in the oxidative dehydrogenation reaction of normal-butane, Or overcome the limitations of the magnesium orthovanadate catalyst supported on zirconia in our previous patent applications [Song In-gyu, Lee Ho-won, Pyeong-sik, Young-jin Cho, Lee Jin-seok, Jang Ho-sik, Korea Patent Application 10-2011-0021037 (2011)] To this end, by using magnesia-zirconia prepared by a special method as a carrier, after magnesium orthovanadate is reduced during the oxidative dehydrogenation reaction of normal-butane using magnesium orthovanadate contained in conventional magnesia Suppresses the disadvantages that are not reoxidized and maintains the yield of catalyst stably. Number, and it is possible to obtain a magnesium climb noodles or higher activity than the catalysts supported on the zirconia date by the prior art patent art. In addition, there is no problem in the processability of the magnesia-zirconia composite carrier, and it is possible to directly perform an oxidative dehydrogenation reaction of normal-butane without a separate activation step under the reaction conditions, and thus it is directly applicable to a commercial process.

The present invention also relates to a method for producing n-butene and 1,3-butadiene through an oxidative dehydrogenation reaction of n-butane on a magnesium orthovanadate catalyst supported on a magnesia-zirconia composite carrier produced by the above method .

The reactant for the oxidative dehydrogenation reaction of n-butane is a mixed gas containing n-butane, oxygen and nitrogen, and is composed of n-butane, oxygen and nitrogen in a volume ratio of 2 to 10: It is preferably contained in a ratio of 40:50 to 97.5, preferably 4: 2 to 20:76 to 94, more preferably 4: 2 to 10:86 to 94. When the volume ratio of n-butane to oxygen and nitrogen is out of the above range, a complete oxidation reaction, which is a side reaction during the oxidative dehydrogenation reaction of n-butane, occurs frequently, the activity of the catalyst is lowered, Which is undesirable.

When the reactant in the form of the mixed gas is supplied to the reactor, the amount of the reactant to be injected can be controlled by using a mass flow controller. The amount of the reactant to be injected is 50 to 5000 h (GHSV) ^-1 , preferably 500 to 3,000 h ^-1 , and more preferably 1000 to 2000 h ^-1 . When the space velocity is less than 50 h ^-1, coking due to reaction by-products of the catalyst may occur or a hot spot may be generated due to the heat released during the reaction, If it is more than 5000h < ^{-1 &} gt ;, the catalytic action can not sufficiently take place while the reactant passes through the catalyst layer.

The reaction temperature for advancing the oxidative dehydrogenation reaction of the n-butane is preferably 300 to 800 ° C, more preferably 450 to 600 ° C, and most preferably 500 ° C. When the reaction temperature is lower than 300 ° C., n-butane is not fully activated, which is not preferable. When it exceeds 800 ° C., decomposition reaction of n-butane is undesirably caused.

According to the present invention, the magnesia-zirconia composite carrier having magnesia formed on zirconia can be prepared using zirconia, which is easily commercially available with zirconia, which can be easily prepared by a simple manufacturing method. Magnesium orsovana based on magnesia-zirconia complex carrier for oxidative dehydrogenation of normal-butane, which can stably prepare normal-butene and 1,3-butadiene in high yield using vanadium salt You can get a dating catalyst. According to the present invention, a magnesium orthovanadate catalyst supported on a magnesia-zirconia composite carrier prepared by supporting magnesium salt in zirconia prepared by gel-oxalate method is used for oxidative dehydrogenation of normal-butane. The problem of deactivation, which is a limitation of the magnesium orthovanadate catalyst according to the prior art, can be solved, and a patent application by the present inventors [Song In Kyu, Lee Ho Won, Yoo Sik, Cho Young Jin, Lee Jin Seok, Jang Ho Sik, Korea Patent Application 10-2011-0021037 (2011)] overcomes the problem of low initial activity, which is the limitation of magnesium orthovanadate catalysts supported on zirconia, and provides a stable and efficient reaction that can continuously obtain high initial activity. It can be carried out to obtain a catalyst that can be applied directly to a commercial process.

According to the present invention, it is possible to manufacture normal-butane and low-use value of normal-butene and 1,3-butadiene, which are gradually increasing in demand and value worldwide as an intermediate of many petrochemical products in the petrochemical industry. As a result, it is possible to achieve high added value of the C4 fraction. In addition, by securing a single production process for the production of normal-butene and 1,3-butadiene without the addition of naphtha crackers, economic benefits can be obtained by meeting the growing demand for normal-butene and 1,3-butadiene. The advantage is that it can proactively cope with future market changes.

1 is a graph showing the results of X-ray diffraction analysis of magnesium orthovanadate catalysts supported on magnesia-zirconia composite carriers prepared by the methods according to Preparation Examples 1, 2 and 3 of the present invention.
Figure 2 is a conventional patent application by the present inventors prepared by the method according to Comparative Preparation Examples 1, 2 of the present invention [Song In-gyu, Lee Ho-won, Pyeong Sik, Young-jin Cho, Lee Jin-seok, Jang Ho-sik, Republic of Korea Patent Application 10-2011-0021037 (2011 X-ray diffraction analysis results of magnesium orthovanadate catalyst supported on zirconia and magnesium orthovanadate catalyst supported on magnesia according to the prior art.
3 is a magnesium orthovanadate catalyst supported on a magnesia-zirconia composite carrier according to Example 1 and Comparative Examples 1 and 2 of the present invention, and the present inventors of the present invention [Song In-gyu, Lee Ho-won, Flexible type] , Myung-Joo Cho, Jin-Suk Lee, Ho-Sik Jang, Korean Patent Application 10-2011-0021037 (2011)], on magnesium orthovanadate catalyst supported on zirconia, and magnesium orthovanadate catalyst supported on magnesia according to the prior art, respectively. After performing the oxidative dehydrogenation reaction of normal-butane for 24 hours, it is a graph which shows the difference in activity for reaction of each catalyst.
4 is a magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier according to Example 1 and Comparative Examples 1 and 2 of the present invention, and the present inventors of the present invention [Song In-gyu, Lee Ho-won, Flexible type , Myung-Joo Cho, Jin-Seok Lee, Ho-Sik Jang, Korean Patent Application 10-2011-0021037 (2011)], on magnesium orthovanadate catalyst supported on zirconia, and magnesium orthovanadate catalyst supported on magnesia according to the prior art. It is a graph showing the change in activity over time and the difference between the oxidative dehydrogenation of each normal-butane.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, these embodiments are for illustrative purposes only, and the present invention is not limited to these embodiments.

[Production Example 1]

Preparation of Zirconia by Gel-Oxalate Method

To prepare 10 g of zirconia, 18.9 g of zirconium chloride was dissolved in ethanol (1000 ml) to make a zirconium ethanol solution, while 24.6 g of oxalic acid dihydrate was dissolved in ethanol (200 ml) to make an oxalic acid ethanol solution. The two solutions that were sufficiently dissolved were injected into the zirconium ethanol solution as slowly as possible by injecting the oxalic acid ethanol solution using a syringe pump, followed by stirring. The mixed solution was stirred at room temperature for 3 hours using a magnetic stirrer so that sufficient stirring was performed, and then left for 12 hours at room temperature for phase separation. The ethanol solution is filtered in a phase-separated mixed solution to remove unnecessary ions such as chloride, and then washed and agitated with an ethanol solution several times. The finally precipitated solution is filtered with a centrifuge, and the obtained solid sample is heated to 80 ° C Lt; / RTI > for 12 hours. The resulting solid sample was heat treated for 3 hours at 550 ° C. in an electric furnace in an air atmosphere to prepare zirconia prepared according to the single-phase gel-oxalate method.

[Production Example 2]

Preparation of Three Magnesia-Zirconia Composite Carriers by Supporting Magnesium Salts

Magnesia-zirconia composite carrier was prepared by supporting magnesium salt in zirconia prepared and prepared by the method according to the gel-oxalate method according to Preparation Example 1, and the molar ratio of magnesia: zirconia was 4: 1, 2: 1, 1: 1. Differently three carriers were prepared. Specific manufacturing method is as follows.

In order to prepare 3 g of magnesia-zirconia composite carrier, 4.7 g, 7.5 g, and 10.8 g of magnesium nitrate hexahydrate were dissolved in a small amount of distilled water, respectively, and each aqueous solution was prepared by the method according to Preparation Example 1. 2.3g, 1.8g and 1.3g were mixed by the general initial impregnation method. The magnesium-containing zirconia sample was dried at 80 ° C. for 12 hours, and the resultant solid sample was heat-treated at an air temperature of 550 ° C. for 3 hours to form magnesium salts with magnesia.

[Production Example 3]

Preparation of Magnesium Orthovanadate Catalyst Supported on Three Magnesia-Zirconia Composite Carriers

0.74 g of ammonium vanadate was dissolved in a small amount of an aqueous solution of oxalic acid dissolved in 1.6 g of oxalic acid, and impregnated with 80 g of vanadium pentoxide in 3 g of the magnesia-zirconia composite carrier obtained by the method of Preparation Example 2, followed by impregnation. After drying for 12 hours to obtain a solid sample, the magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier was prepared by maintaining the temperature of 550 ℃ in an air atmosphere electric furnace for 3 hours. The catalyst prepared through the above process was named VMgO / MgZrO ₄ , VMgO / MgZrO ₂ , VMgO / MgZrO ₁ , respectively, according to the molar ratio of magnesia: zirconia (4: 1, 2: 1, 1: 1).

The phase of the prepared catalyst was confirmed through X-ray diffraction analysis, and the results are shown in FIG. 1. As shown in FIG. 1, as a result of the surface analysis of the magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier prepared by the method of Preparation Examples 1, 2, and 3 of the present invention, the catalysts were all monoclinic zirconia and magnesia. It is speculated that the characteristic small intensity peaks of magnesium orthovanadate are present as a slightly developed phase in the mixed carrier of two phases, but the properties of monoclinic zirconia and magnesia are very well developed and easy to confirm. Sovanadate is observed in a small intensity over a wide range of characteristics, so it was not possible to confirm the exact image only by confirming the wide distribution of small phases in the range.

The component ratio and surface area of the magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier prepared by the method according to Preparation Examples 1, 2, and 3 were confirmed by ICP elemental analysis and BET surface area analysis. Indicated. As shown in Table 1, the analysis of the elemental component ratio of the catalyst showed close to the theoretical value calculated during the preparation of the catalyst, which could not be confirmed by the X-ray diffraction analysis, but the formation of magnesium orthovanadate catalyst could be judged. there was.

[Table 1]

Comparative Preparation Example 1

Preparation of Magnesium Orthovanadate Catalyst Supported on Zirconia

For comparison with the magnesium orthovanadate catalyst supported on magnesia-zirconia according to the present invention, the present inventors of the present invention [Song In Kyu, Lee Ho Won, Yoo Sik, Cho Young Jin, Lee Jin Seok, Jang Ho Sik, Korea Patent Application 10-2011-0021037 ( 2011)] to prepare a magnesium orthovanadate catalyst supported on zirconia. The preparation method of the catalyst is as follows.

To 2.6 g of zirconia prepared and prepared by the method according to the gel-oxalate method according to Preparation Example 1, an aqueous magnesium salt solution in which 2.4 g of magnesium nitrate hexahydrate was dissolved in a small amount of distilled water was mixed by the impregnation method. At this time, the weight of the magnesium salt was only for the formation of magnesium orthovanadate, and it was determined that there was no magnesium present as magnesia since the catalyst was finally made. The magnesium-containing zirconia sample was dried at 80 ° C. for 12 hours, and the resultant solid sample was heat-treated at an air temperature of 550 ° C. for 3 hours to form magnesium salts with magnesia. 0.74 g of ammonium vanadate was dissolved in a small amount of an aqueous solution of oxalic acid containing 1.6 g of oxalic acid so that 3 g of the resulting magnesia-zirconia composite carrier was 16 wt% of vanadium pentoxide, and impregnated, followed by drying at 80 ° C. for 12 hours. After obtaining, the magnesium orthovanadate catalyst supported on zirconia was prepared by heat treatment for 3 hours while maintaining the temperature of 550 ℃ in an electric furnace of an air atmosphere. The catalyst prepared through the above process was named VMgO / ZrO ₂ .

[Comparative Production Example 2]

Preparation of Magnesium Orthovanadate Catalyst Supported in Magnesia

For comparison with the magnesium orthovanadate catalyst supported on magnesia-zirconia according to the present invention, a magnesium orthovanadate catalyst supported on magnesia was prepared by a conventional technique. The preparation method of the catalyst is as follows.

0.74 g of ammonium metavanadate was quantified in an amount of vanadium pentoxide based on 16% by weight of the total catalyst, dissolved in ammonia water, and then impregnated with 3 g of magnesia, which is commercially available as a carrier for the catalyst. The sample obtained was dried at 80 ° C. for 12 hours to obtain a solid sample, followed by heat treatment for 3 hours at 550 ° C. in an electric furnace in an air atmosphere, whereby magnesium and vanadium ions reacted with magnesium orthovanadate catalyst supported on magnesia. It was formed to be. The obtained catalyst was named VMgO / MgO.

X-ray diffraction analysis results of the magnesium orthovanadate catalyst supported on zirconia according to Comparative Preparation Example 1 and X of the magnesium orthovanadate catalyst supported on magnesia prepared by the method according to Comparative Preparation Example 2 The results of the line diffraction analysis are shown together. As shown in FIG. 1, the characteristics of the carriers of zirconia and magnesia can be well confirmed, but the magnesium orthovanadate phase, which is an active ingredient of the catalyst, could not be identified because it is obtained as a small phase in a wide range. In FIG. 2, since the X-ray diffraction pattern analysis result of the magnesium orthovanadate catalyst supported on the zirconia made by the method of Comparative Preparation Example 1 did not show the intrinsic properties of magnesia, all the supported magnesium during manufacture was magnesium orsoba Judging from the fact that it was used to form the nadate catalyst phase is consequently not wrong. Accordingly, the catalyst prepared by the method according to Comparative Preparation Example 1 was determined to be different from the magnesia-zirconia composite carrier according to the present invention.

ICP elemental analysis and BET surface area analysis were performed on the component ratios and surface areas of the magnesium orthovanadate catalyst supported on zirconia according to Comparative Preparation Example 1 and the magnesium orthovanadate catalyst supported on magnesia prepared by Comparative Preparation Example 2. It was confirmed through, and the results are shown in Table 2.

As shown in Table 2, the analysis of the elemental component ratio of the catalyst showed close to the theoretical value calculated during the preparation of the catalyst, which could not be confirmed by the X-ray diffraction analysis. , Magnesium orthovanadate phase was formed, but according to the characteristics of the X-ray diffraction pattern was not confirmed because of the small, it was determined that it was formed with magnesium orthovanadate.

[Table 2]

Example 1

Oxidative dehydrogenation of n-butane via continuous-flow catalytic reactor

The oxidative dehydrogenation of normal-butane was carried out using a magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier prepared by the method of Preparation Example 3, and specific reaction experimental conditions are as follows.

The reactant used in the oxidative dehydrogenation of normal-butane in Example 1 is a C4 mixture containing 99.4% by weight of normal-butane, and its composition is shown in Table 3 below.

[Table 3]

As a reactant, the C4 mixture was injected in the form of a mixed gas with oxygen and nitrogen.

The composition ratio of the reactants was set based on the normal-butane amount in the C4 mixture, with the ratio of normal-butane: oxygen: nitrogen being 4: 8: 88.

In the reaction, the catalyst powder is fixed in a straight quartz reactor for catalytic reaction, the reactor is installed in an electric furnace to maintain a constant reaction temperature of the catalyst bed, and the reaction proceeds continuously while passing the catalyst bed in the reactor. It was.

The injection rate of the reactants was reacted by setting the amount of catalyst to be 2000 h ⁻¹ based on normal-butane. The temperature of the fixed-bed reactor was raised from room temperature to 500 ° C by flowing nitrogen and oxygen before flowing the reactant, and the catalyst was activated so that the reaction temperature of the catalyst bed temperature of the fixed bed reactor was 500 ° C And the reaction was carried out. After the reaction, the products include normal-butene and 1,3-butadiene, which are the main products of the reaction, and non-reacted normal-butane by-products such as carbon dioxide due to complete oxidation, by-product from cracking, and by-product from isomerization reaction. As a result, gas chromatography was used to separate and analyze them. The conversion of normal-butane, the selectivity of the dehydrogenation reaction product, and the yield of the dehydrogenation reaction product on the magnesium orthovanadate catalyst supported on zirconia or magnesia are given by the following equation. Calculated by 2 and 3.

[Equation 1]

&Quot; (2) "

&Quot; (3) "

The oxidative dehydrogenation of normal-butane was carried out for 24 hours on a magnesium orthovanadate catalyst supported on three magnesia-zirconia composite carriers prepared in Preparation Example 3, and the reaction proceeded 24 hours after the reaction proceeded. The experimental results are shown in Table 4 and FIG. 3, and the reaction activity trends with time for 24 hours are shown in FIG. 4.

[Table 4]

Comparative Example 1

On zirconia Supported  magnesium Orthovanadate  Of catalysts Oxidative  Dehydrogenation activity

For comparison with the activity result of the oxidative dehydrogenation reaction through the magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier carried out by the method according to Example 1 of the present invention, by the method according to Comparative Preparation Example 1 The oxidative dehydrogenation of normal-butane was carried out in the order according to Example 1, using a magnesium orthovanadate catalyst supported on pure zirconia, reported in the inventors' prior patent application. The results of the reaction experiments according to Comparative Example 1 are shown in Table 5, and the results shown in Table 5 were carried out in the oxidative dehydrogenation reaction of normal-butane through magnesium orthovanadate catalyst loaded on zirconia as in Example 1 The result of the reaction after performing for a time.

[Table 5]

When the magnesium orthovanadate catalyst supported on pure zirconia and the magnesium orthovanadate catalyst supported on magnesia-zirconia composite carrier were used for oxidative dehydrogenation reaction, the pure zirconia carrier and magnesia-zirconia on magnesium orthovanadate catalyst The results of the reaction experiments according to Example 1 and Comparative Example 1 were compared to observe the difference of the complex carriers on the reaction activity, and the results of the reaction experiments after the oxidative dehydrogenation of normal-butane for 24 hours were performed. 6 and 3 together.

TABLE 6

Referring to Table 6 and FIG. 3, in the case of the magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier in the catalytic activity experiment conducted by each catalyst, all three types of magnesium orthovanadate catalysts supported on pure zirconia It showed higher activity, and thus the magnesia-zirconia complex carrier was judged to be more suitable as a carrier for the catalyst for oxidative dehydrogenation of normal-butane than a pure zirconia carrier. In the case of the magnesia-zirconia composite carrier, it was thought that the advantages of two catalysts, a catalyst using pure magnesia as a carrier and a catalyst using pure zirconia as a carrier, showed synergistic effects by using a carrier mixed with magnesia and zirconia. In the prior patent application of the present inventors [Song In-gyu, Lee Ho-won, Pyeon-sik, Young-jin Cho, Lee Jin-seok, Jang Ho-sik, Republic of Korea Patent Application 10-2011-0021037 (2011)], the use of pure magnesia as a carrier can obtain a high initial activity but inactivated On the other hand, when pure zirconia is used as a carrier, stable activity can be obtained, but lower activity was required than when magnesia was used as a carrier. On the contrary, when the magnesia-zirconia composite carrier in the form of a mixture of two carriers according to the present invention is used as a carrier of magnesium orthovanadate catalyst, it is possible to obtain higher activity than magnesium orthovanadate catalyst supported on pure zirconia. It is expected that the synergistic effect of the magnesia contained in the carrier as described above, which is an effect of the magnesia-zirconia complex carrier according to the present invention, than the magnesium orthovanadate catalyst supported in the conventional zirconia by the present invention High activity can be expected.

3 shows the results of the oxidative dehydrogenation of the magnesium orthovanadate catalyst supported on magnesia carried out according to Comparative Example 2, but it has very low activity compared to the other four catalysts. I never do that.

Comparative Example 2

Oxidative Dehydrogenation Activity of Magnesium Orthovanadate Catalysts Supported in Magnesia

For comparison with the activity result of the oxidative dehydrogenation reaction through the magnesium orthovanadate catalysts supported on the magnesia-zirconia composite carrier carried out by the method according to Example 1 of the present invention, the magnesium ore supported on magnesia Sovanadate catalyst was prepared by the method according to Comparative Preparation Example 2, and the oxidative dehydrogenation reaction of normal-butane was carried out in the order of Example 1, and the result of the reaction experiment after performing the oxidative dehydrogenation reaction for 24 hours. Is shown in Table 7.

[Table 7]

From the results of the oxidative dehydrogenation of magnesium orthovanadate catalyst supported on magnesia and magnesium orthovanadate catalyst supported on magnesia-zirconia composite carrier, magnesium and magnesia-zirconia were used as carriers in magnesium orthovanadate catalyst, respectively. When used, the results of the reaction experiments according to Example 1 and Comparative Example 2 were compared to observe the difference on the reaction activity according to the reaction time. 4 is shown.

[Table 8]

Referring to Table 8 and FIG. 4, in the case of the magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier in the catalytic activity experiment conducted by each catalyst, all three types of magnesium orthovanadate catalysts supported on magnesia It can be seen that, while exhibiting high initial activity and rapidly deactivating at some point, almost losing activity as a catalyst, the initial activity is maintained. Accordingly, the magnesia-zirconia composite carrier was judged to be more suitable as a carrier for the catalyst for oxidative dehydrogenation of normal-butane than a pure magnesia carrier. This is because, as described above, the magnesia-zirconia complex carrier is a carrier capable of achieving synergistic effects by taking the advantages of magnesia and zirconia carriers, respectively, and is supported on magnesia having a high initial activity but limiting rapid inactivation. Zirconia, which can obtain high reaction stability to the magnesium orthovanadate catalyst, is used as a carrier, and a new catalyst having both advantages of initial activity and reaction stability has been developed by the present invention. have.

The reaction activity trend of the magnesium orthovanadate catalyst supported on pure zirconia carried out by Comparative Example 1 with time is shown in Table 8 and FIG. 4, but no change was found during the reaction.

Claims (9)

A process for preparing a magnesia-zirconia composite carrier for oxidative dehydrogenation reaction of normal-butane, comprising the following steps:
(a) dissolving a zirconium precursor and oxalic acid in alcohol to prepare a zirconium alcohol solution and an oxalic acid alcohol solution, respectively;
(b) synthesizing zirconia by mixing the zirconium alcohol solution and the oxalic acid alcohol solution prepared in step (a);
(c) separating, drying and heat-treating zirconia as a solid component from the resultant solution obtained in step (b) to obtain zirconia for the preparation of the magnesia-zirconia composite carrier;
(d) impregnating an aqueous solution of magnesium salt in the zirconia obtained in step (c); And
(e) drying and heat-treating the resultant obtained in step (d) to obtain a magnesia-zirconia composite carrier for oxidative dehydrogenation reaction catalyst of normal-butane. The magnesia-zirconia for catalytic oxidation of normal-butane according to claim 1, wherein the zirconium and oxalic acid used in step (a) are used in a molar ratio of zirconium: oxalic acid = 1: 2 to 5. Method for producing a composite carrier. The method of claim 1, wherein the drying in the step (c) is carried out for 3 to 24 hours at 50 ~ 200 ℃, heat treatment is carried out 1 to 12 hours at 350 ~ 800 ℃ oxidative product of normal-butane Method for producing magnesia-zirconia composite carrier for dehydrogenation reaction catalyst. The magnesia-zirconia catalyst for the oxidative dehydrogenation reaction of normal-butane according to claim 1, wherein the molar ratio of magnesia: zirconia in the magnesia-zirconia composite carrier prepared in step (d) is 0.5-16: 1. Method for producing a composite carrier. A method for preparing a magnesium orthovanadate catalyst supported on a magnesia-zirconia composite carrier, comprising the following steps:
(i) impregnating the aqueous solution of vanadium salt into the magnesia-zirconia composite carrier prepared by the method of any one of claims 1 to 4;
(ii) drying and heat-treating the resultant obtained in step (i) to obtain a magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier. The method of claim 5, wherein the heat treatment in the step (ii) is prepared for magnesium orthovanadate catalyst supported on the magnesia-zirconia composite carrier, characterized in that performed for 1 to 12 hours at a temperature of 350 ~ 800 ℃ Way. A method for preparing normal-butene and 1,3-butadiene comprising performing oxidative dehydrogenation of normal-butane on a magnesium orthovanadate catalyst supported on a magnesia-zirconia composite carrier prepared by the method of claim 5. . The reaction product of the oxidative dehydrogenation of normal-butane is a mixture of normal-butane, oxygen and nitrogen in a volume ratio of normal-butane: oxygen: nitrogen = 2 to 10: 0.5 to 40:50 to 97.5. Method for producing a normal-butene and 1,3-butadiene, characterized in that the mixed gas. 8. The process for producing normal-butene and 1,3-butadiene according to claim 7, wherein the oxidative dehydrogenation of normal-butane is carried out at a reaction temperature of 300 to 800 deg.

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