KR101437744B1 - Method of producing n-butane and 1,3-butadiene using magnesium orthovanadate catalyst for oxidative dehydrogenation of n-butane using oxygen and carbon dioxide as oxidant - Google Patents

Abstract

The present invention relates to a process for preparing a magnesium orthovanadate catalyst for the oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as oxidizing agents, and a process for producing n-butene and 1,3-butadiene using the catalyst.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing n-butene and 1,3-butadiene using a magnesium orsorbanate catalyst for oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as oxidizing agents. using magnesium orthovanadate catalyst for oxidative dehydrogenation of n-butane using oxygen and carbon dioxide as oxidant}

The present invention relates to a process for preparing a magnesium orthovanadate catalyst for the oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as oxidizing agents, and a process for producing n-butene and 1,3-butadiene using the catalyst.

As an intermediary for many petrochemical products in the petrochemical industry, the production of light olefins, which is an important basic raw material whose demand and value are gradually increasing globally, is a national infrastructure industry. It is an energy-intensive type that accounts for about 40% Industry. The reason for such high energy consumption for producing light olefins is that most of the light olefins currently produced are obtained through a naphtha steam cracking process which requires high temperature reaction conditions to perform the process. Nitrogen-butene and 1,3-butadiene supplied to the present market are mostly supplied by such naphtha cracking. In this situation, the capacity of naphtha cracking has a very small influence on the supply and demand of n-butene and 1,3-butadiene It can be said that it is big.

However, the naphtha cracking process is not a sole process for producing n-butene and 1,3-butadiene due to the nature of the process for producing a basic oil such as ethylene and propylene, and thus n-butene and 1,3-butadiene Naphtha crackers can not be newly added or expanded to expand production, and even if naphtha crackers are added, other basic oils other than n-butene and 1,3-butadiene are produced in surplus. In addition, due to recent trends in the petrochemical market, the demand for ethylene and propylene has greatly increased, and the cracking process is shifting toward higher yields. In addition, the price of naphtha raw material that can obtain C4 oil is steadily rising, and the yield of C4 oil is low, but the process of using light hydrocarbons such as ethane and propane, which yields higher yields for other basic oils such as ethylene and propylene , And it is becoming increasingly difficult to secure the C4 mixture, especially n-butene and 1,3-butadiene, through the naphtha cracking process because the naphtha cracking process ratio is relatively reduced.

As mentioned above, the naphtha cracking process accounts for most of the n-butene and 1,3-butadiene feeds, but due to the above-mentioned reasons, the supply-demand imbalance due to the recent increase in the demand for n-butene and 1,3- It can not be an effective alternative. Accordingly, various studies have been made on the production techniques of n-butene and 1,3-butadiene not through naphtha crackers, and dehydrogenation reaction in which hydrogen is removed from n-butane to obtain n-butene and 1,3-butadiene Butene and 1,3-butadiene, which can quickly cope with recent market changes, have been attracting attention as a sole process for producing n-butene and 1,3-butadiene (Non-Patent Documents 1 to 4).

The dehydrogenation reaction of n-butane removes hydrogen from n-butane to produce n-butene and 1,3-butadiene. It is a direct dehydrogenation reaction that removes hydrogen directly from n-butane, Butane, and an oxidative dehydrogenation reaction to remove hydrogen from butane. The direct dehydrogenation reaction of n - butane is disadvantageous in that it requires a high temperature reaction condition due to thermodynamically unfavorable endothermic reaction and consumes a lot of energy. In addition, a highly efficient noble metal catalyst such as platinum or palladium is used to carry out the reaction. However, in the case of such a noble metal catalyst, there is a disadvantage that the lifetime of the noble metal catalyst is very short and the regeneration process must be performed (Patent Documents 1 and 2).

On the other hand, the oxidative dehydrogenation reaction of n-butane is different from the direct dehydrogenation reaction in that n-butane reacts with oxygen to convert n-butene to water or 1,3-butadiene and water, But it is thermodynamically advantageous in comparison with the direct dehydrogenation reaction of n-butane, and the generated water due to the catalytic reaction can suppress the water generated after the reaction, so that the rapid temperature change of the catalytic layer can be prevented. Therefore, the oxidative dehydrogenation reaction of n-butane can be operated under favorable process conditions rather than the direct dehydrogenation process. If a suitable high efficiency catalytic process is developed, this process can save energy, -Butene and 1,3-butadiene. ≪ / RTI >

According to the above-mentioned, the oxidative dehydrogenation reaction of n-butane is thermodynamically advantageous in comparison with the direct dehydrogenation reaction of n-butane, so that higher yields of n-butene and 1,3-butadiene are obtained even under mild reaction conditions It is expected that many side reactions such as high oxidation reaction in which carbon monoxide or carbon dioxide occurs can be expected because oxygen is used as a reactant. Therefore, the oxidative dehydrogenation reaction of n-butane is to develop a catalyst capable of enhancing the selectivity of n-butene and 1,3-butadiene while suppressing side reactions such as complete oxidation reaction while enhancing the conversion of n-butane It is important.

In the oxidative dehydrogenation reaction of n-butane, the addition of carbon dioxide as an oxidizing agent and the use of carbon dioxide and oxygen as oxidizing agents can reduce the selectivity and production amount of carbon dioxide, which is a main by-product, and reduce the content of n-butene and 1,3- It is known that the yield and production amount of butadiene can be increased. This is because when oxygen and carbon dioxide are used as the oxidizing agents, the adsorption of oxygen and carbon dioxide in the active sites is competitively performed, and the adsorption amount of oxygen is decreased, and the carbon dioxide acts as a catalyst poison to the non-selective sites of the catalyst surface, And it is reported that it reduces peroxidation (Non-Patent Documents 5 to 6).

As catalysts known to be effective for the production of n-butene and 1,3-butadiene by the oxidative dehydrogenation reaction of n-butane, there have been proposed magnesium ororbanadate catalysts (Non-Patent Documents 4 and 6 to 9, 3 to 7), vanadium oxide-based catalysts (non-patent documents 10 to 11 and patent document 8), pyrophosphate catalysts (non-patent documents 2 and 5), ferrite catalysts (non-patent documents 12 and 9) Nickel-based catalysts (Non-Patent Document 13), and the like.

A common feature of these complex oxide catalysts is that they include transition metals, because electron transfer between the catalyst and n-butane must be possible through oxidation-reduction of the catalyst (Non-Patent Document 14). The catalysts may include an oxidative-reducible metal such as vanadium, iron, nickel, titanium, etc. to perform an oxidative dehydrogenation reaction of n-butane. In particular, The activity of the catalysts is known to be high, so that the oxidation-reduction ability of the vanadium metal can be judged to be suitable for the oxidative dehydrogenation reaction of n-butane (Non-patent Documents 7 to 8).

In general, the above-mentioned magnesium orobarnadate catalyst is prepared in the form of a metal oxide containing magnesium orthovanadate (Mg ₃ (VO ₄ ) ₂ ), which is an active magnesium oxide orobasilicate catalyst containing no magnesia, Has been reported to be less active than magnesium orsorbanate, including magnesia. The results of oxidation-dehydrogenation reaction of n-butane using a pure magnesium orthovanadate catalyst have been reported in conventional patents and literatures. Specifically, the reactant injection ratio is n-butane: oxygen: helium = 5: 10: Butane oxidative dehydrogenation reaction was carried out at 540 ° C. by using a magnesium orsorbanadate catalyst not supported at 85 ° C. (Non-Patent Document 4), and it was reported that the dehydrogenation product yield was 5.7% It was reported that the reactant injection ratio was 11.5% of n-butane conversion and 6.7% of dehydrogenation product yield through reaction at 540 ° C under the conditions of n-butane: oxygen: helium = 4: 8: 88 9).

In the case of the magnesium orsorbanate catalyst including the magnesia, the activity can be further improved. The magnesium orsorbanate catalyst containing the magnesia, which is obtained by supporting vanadium in an excessive amount of magnesia, can be used in an oxidative dehydrogenation reaction of n-butane Have been reported to exhibit good activity. Specifically, the oxidative dehydrogenation reaction of n-butane was carried out under the conditions of a reaction temperature of 550 ° C. and a normal-butane: oxygen: helium ratio of 5:20:75 in the reactants. As a result, the conversion of n-butane to 25.7% It was reported that the dehydrogenation reaction product selectivity of 61.2% and the dehydrogenation product yield of 15.7% were obtained (non-patent document 15), and the reactant injection ratio was n-butane: oxygen: helium = 5: Butane conversion of 55.7%, selectivity of dehydrogenation reaction product of 36.8%, and yield of 20.5% were obtained under the conditions of a temperature of 550 ° C. (Non-Patent Document 16).

Butene and 1,3-butadiene, which are products of dehydrogenation reaction, can be obtained in a high yield by improving the activity of the magnesium orbovanadate catalyst supported on the magnesia to the oxidative dehydrogenation reaction of n-butane through an additive A literature on the utilization of magnesium orthobarnadate catalysts has been reported (Non-Patent Document 17). In this document, titanium oxide and chromium oxide are mixed with 25 wt% magnesium orthovanadate catalyst supported on magnesia, and 570 Butane conversion of 54.0% and a dehydrogenation product yield of 33.8% at the normal-butane: oxygen: nitrogen ratio of 4: 8: 88. In addition, when the catalyst containing magnesium or oresorbadate as an additive to magnesium orbovanade supported on magnesia was applied to the oxidative dehydrogenation reaction of n-butane, the reactant injection ratio was changed from n-butane: oxygen: helium = 5: 20: Butane oxidation reaction at 550 ° C using a catalyst under the condition of 75%, the conversion of n-butane to 49.2%, the selectivity to dehydrogenation reaction of 47.6%, and the yield of dehydrogenation reaction product of 23.4% (Non-patent document 16).

It has been reported that dehydrogenation products can be obtained at a higher selectivity and yield than in the case of using only oxygen as the oxidizing agent when the magnesium orobarnadate catalyst is used in the oxidative dehydrogenation reaction of n-butane in which carbon dioxide and oxygen are used as the oxidizing agents (Non-Patent Document 6). In this document, a magnesium orsorbanadate catalyst supported on magnesia was reacted at a reaction temperature of 600 ° C under a condition of a normal-butane: oxygen: carbon dioxide: nitrogen ratio of 4: 6: 30: Butane conversion, 70.2% dehydrogenation reactant selectivity, and 34.1% dehydrogenation product yield.

The magnesia-supported magnesium orthovanadate catalyst can obtain n-butene and 1,3-butadiene in a high yield in the oxidative dehydrogenation reaction of n-butane, but must be reversible in the course of the catalytic reaction Since the oxidation-reduction of the catalyst is partially irreversible (Non-Patent Document 1), high activity of the magnesium orsorbanadate catalyst supported on the magnesia is not maintained for a long time, and thus it has been limited to utilize it as a commercial process.

Therefore, the inventors of the present invention have found that, by continuous research, it is possible to provide a magnesium oresorbitanate catalyst that exhibits thermal and chemical properties without any problems such as reduction in activity over time of magnesium orsorbanate catalyst supported on magnesia and low activity of other vanadium- Catalysts for the preparation of n-butene and 1,3-butadiene in a stable and high yield by using techniques for the preparation of stable magnesium and zirconia-incorporated magnesium orthovanadate catalysts, (Patent Documents 3 to 7). In the above patents, the inventors of the present invention have found that a magnesium oresorbanadate catalyst containing magnesia and zirconia for a catalyst for oxidative dehydrogenation of n-butane can be produced by a single stage sol-gel method, a gel-oxalate coprecipitation method, a sol- The catalytic process was developed to obtain n-butene and 1,3-butadiene with stable and high activity through oxidative dehydrogenation reaction of n-butane.

[Prior Art Literature]

[Patent Literature]

Patent Document 1: US 6,433,241 B2 (A. Wu, C. A. Frake) 2002.8.13.

Patent Document 2: US 6,187,984 (A. Wu, C.A. Frake) 2001.2.13.

Patent Document 3: Korean Patent Application 10-2011-0021037, filed on Mar. 09, 2011

Patent Document 4: Korean Patent Application 10-2011-0051293, filed on May 30, 2011

Patent Document 5: Korean Patent Application 10-2011-0101954, filed on October 6, 2011

Patent Literature 6: Korean Patent Application 10-2012-0006693, filed on 2012. 01. 20

Patent Literature 7: Korean Patent Application 10-2012-0086839, filed on 08.08.2008

Patent Document 8: US 3,914,332 (A.F. Dickason) 1975.10.21.

Patent Document 9: US 3,303,234 (L. Bajars, L. J. Croce) 1967.2.7.

[Non-Patent Document]

Non-Patent Document 1: N. Kijima, M. Toba, Y. Yoshimura, Catal. Lett., Vol. 127, p. 63 (2009).

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Non-Patent Document 4: A.A. Lemonidou, G.J. Tjatjopoulos, I.A. Vasalos, Catal. Today, vol. 45, p. 65 (1998).

Non-Patent Document 5: F. Urlan, I.C. Marcu, I. Sandulescu, Catal. Commun., Vol. 9, p. 2403 (2008).

Non-Patent Document 6: S. Ge, C. Liu, S. Zhang, Z. Li, Chem. Eng. J., 94, 121 (2003).

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Non-Patent Document 12: 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).

Non-Patent Document 13: L.M. Madeira, R.M. Martin-Aranda, F.J. Maldonado-Hodar, J.L.G. Fierro, M.F. Portela, J. Catal., Vol. 169, p. 469 (1997).

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Accordingly, an object of the present invention is to provide a process for producing a catalyst containing magnesia and zirconia in an active material composed of magnesium orobarnadate, and a magnesium or orobanate catalyst prepared by reacting n-butane in which carbon dioxide and oxygen are used as an oxidizing agent Butane and 1-butene in which the activity of the active ingredient of magnesium or orsubanate is not lowered even when applied to an oxidative dehydrogenation reaction, using n-butane as an oxidizing agent, Butane and 1,3-butadiene from n-butane which can obtain high selectivity and yield of 3-butadiene and low selectivity of carbon dioxide which is a by-product.

In order to solve the above problems, the present invention provides a process for preparing a magnesium orthovanadate catalyst for an oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as oxidizing agents, comprising the steps of:

(a) dissolving a magnesium precursor and a zirconium precursor in a first solvent to prepare a mixed precursor solution of magnesium and zirconium;

(b) dissolving the solid acid in a second solvent to produce a solid acid solution;

(c) mixing the mixed precursor solution of magnesium and zirconium prepared in step (a) and the solid acid solution prepared in step (b) to prepare a mixed solid acid precursor solution;

(d) dissolving the vanadium precursor and the solid acid in a third solvent to prepare a vanadium precursor solution;

(e) mixing the mixed solid acid precursor solution prepared in step (c) and the vanadium precursor solution prepared in step (d) to prepare a catalyst-forming solution; And

(f) thermally drying the catalyst-forming solution to obtain a solid material, followed by heat treatment to obtain a magnesium orobanadate catalyst for oxidative dehydrogenation reaction of n-butane.

In the method of the present invention, the step (e) may further include adding ethylene glycol to the catalyst-forming solution prepared in the step (e) before the step (f) .

The magnesium precursor and the zirconium precursor used in the step (a) may be any precursor that is commonly used. Generally, the precursor of magnesium is a precursor of magnesium, a precursor of magnesium, a precursor of nitrate, It is preferable to use at least one selected from the group consisting of chloride precursors, oxynitrate precursors and oxychloride precursors of zirconium. Magnesium nitrate, And zirconium oxynitrate are particularly preferably used.

The use ratio of the magnesia precursor and the zirconium precursor used in the step (a) is not particularly limited. However, in order to manufacture a magnesium orobonate catalyst capable of stably maintaining the high activity for a long time for the purpose of the present invention, The molar ratio is preferably 0.5 to 16: 1, more preferably 1 to 16: 1.

The first solvent, the second solvent and the third solvent used in the steps (a), (b) and (d) may be the same or different and may be selected from water or an alcohol, It is not.

The solid acid used in the steps (b) and (d) may be selected from the group consisting of citric acid, succinic acid, malic acid and tartaric acid, but is not limited thereto.

In order to convert both the magnesium ion and the zirconium ion into the magnesium stearate and the zirconium solid acid salt in the step (c), the amount of the solid acid dissolved in the second solvent in the step (b) may be the sum of the solid acid: magnesium precursor and the zirconium precursor The molar ratio is preferably 0.5 to 2: 1, more preferably 1: 1, but when added at a molar ratio of less than 0.5: 1, there is a problem that the dispersing ability is lowered, The viscosity is increased, which is not preferable.

The vanadium precursor used in the step (d) may be a conventionally used vanadium salt. For example, it is preferable to use ammonium metavanadate. However, the present invention is not limited thereto. And may further include other vanadium salts conventionally used according to purposes. However, when ammonium metavanadate is used as a vanadium salt, ammonium ion is preferably synthesized, dried and then removed through a heat treatment process so that the influence of ions can be reduced to the maximum.

The molar ratio of the solid acid to the vanadium precursor is preferably 0.5 to 2: 1, more preferably 1: 1, in order to convert the vanadium ion to the vanadium solid acid salt in the step (d) , The addition of a compound having a molar ratio of less than 0.5: 1 causes a problem that the dispersing ability is lowered. On the other hand, when the molar ratio exceeds 2: 1, the viscosity increases, which is not preferable.

The ethylene glycol used in the step (e ') is reacted with a solid acid salt to further stabilize the catalyst-forming solution. The amount of ethylene glycol used in the step (e' The molar ratio of ethylene glycol to solid acid is preferably 0.5 to 4: 1, more preferably 1 to 2: 1, and more preferably 0.5 to 1: 1. When the molar ratio of ethylene glycol to solid acid is less than 0.5: 1, There is a problem of loss of the catalyst. On the other hand, when the ratio exceeds 4: 1, a large amount of energy is required in the heat treatment process, which is not preferable because a magnesium orsorbanate catalyst is not sufficiently synthesized.

In the step (f), the thermal drying may be performed at a temperature ranging from 40 to 200 ° C., and may be performed through a two-step process as follows: In the first step, the catalyst- The composite metal oxide precursor is thermally dried at a temperature of 100 to 200 DEG C for 2 hours or more, preferably 2 to 5 hours as a second step . The thermal drying can remove the first solvent, the second solvent, the third solvent, and by-products such as NO _x . If the thermal drying temperature is within the range of 40 to 200 ° C, the first solvent, The solvent, the third solvent and the by-product gas such as NO _x can be completely removed.

The heat treatment in step (f) may be carried out at a temperature ranging from 400 to 1000 ° C. for 1 to 12 hours, preferably at a temperature ranging from 500 to 700 ° C. for 3 to 6 hours to obtain magnesium oresorbate Catalyst is obtained. The heat treatment of the dried solid sample is not only for changing the solid acid salt of vanadium, magnesium and zirconium to magnesium orthovanadate, magnesia and zirconia, but also considering the reaction temperature of the oxidative dehydrogenation reaction of n-butane, When the heat treatment temperature is less than 400 DEG C or the heat treatment time is less than 1 hour, the vanadium solid acid salt, the magnesium solid acid salt and the zirconium solid acid salt are sufficiently dissolved in the magnesium oresorbane It is not preferable that the temperature is not changed to the temperature, the date, the magnesia and the zirconia. When the heat treatment temperature exceeds 1000 ° C. or the heat treatment time exceeds 12 hours, the crystalline phase of the magnesium orsorbanate catalyst changes, It is not desirable because there is concern .

The vanadium content of the magnesium orobarnadate catalyst prepared as described above is preferably 4.2 to 11.2% by weight based on the total weight of the catalyst for stable and high activity.

The catalyst comprising the magnesium orsorbanadate catalyst of the present invention as described above can be used in the oxidation-dehydrogenation reaction of n-butane by introducing magnesia and zirconia according to the prior patents of the present inventors (Patent Documents 3 to 7) As a method for producing a magnesia orobasilicate catalyst, the present invention applies the above-described catalyst to an oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as an oxidizing agent, without using only oxygen as an oxidizing agent . According to the present invention, the magnesium orobanadate catalyst prepared by the above method is applied to an oxidative dehydrogenation reaction of n-butane in which carbon dioxide and oxygen are used as an oxidizing agent to obtain higher yields of n-butene and 1,3-butadiene And selectivity of low carbon dioxide can be obtained, which is more advantageously applicable to commercial processes.

The reaction product of the oxidative dehydrogenation reaction using the carbon dioxide and oxygen of the n-butane as the oxidizing agent is a mixed gas containing n-butane and oxygen, carbon dioxide and nitrogen, and is a mixture of normal-butane: oxygen: carbon dioxide : Nitrogen in a volume ratio of 2 to 10: 0.5 to 30:20 to 30:30 to 77.5, preferably 4: 2 to 16:20 to 30:50 to 74, more preferably 4: 2 to 10:26, 30: 56-68. ≪ / RTI > When the volume ratio of n-butane, oxygen, carbon dioxide, and nitrogen is out of the above range, carbon dioxide, which is a side reaction during the oxidative dehydrogenation reaction of n-butane, is often generated or 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 1 to 140 ml (weight hourly space velocity (WHSV) Min ^-1 g _cat ^-1 , preferably 10 to 85 ml · min ^-1 g _cat ^-1 , more preferably 25 to 60 ml · min ^-1 g _cat ^-1 . When the space velocity is less than ¹ ml · min ^-1 g _cat ^-1, coking due to reaction by-products of the catalyst occurs or the hot spot is generated due to the heat released during the reaction, And it is not preferable that the reaction amount exceeds 140 ml · min ^-1 g _cat ^-1 because 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 n-butane using carbon dioxide and oxygen as an oxidizing agent is preferably 300 to 800 ° C, more preferably 450 to 600 ° C, more preferably 560 ° C desirable. 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 magnesium orobarnadate catalyst can be easily prepared through a simple synthesis route, and excellent reproducibility can be secured in the production of catalyst. Thus, it is possible to reduce the generation of carbon dioxide and improve the yield of n-butene and 1,3- It is possible to stably obtain a magnesium orobonate catalyst for oxidative dehydrogenation reaction of n-butane in which butadiene can be produced using carbon dioxide and oxygen as oxidants.

According to the present invention, it is possible to produce n-butene and 1,3-butadiene, which are increasing in demand and value as a mediator of many petrochemical products in the petrochemical industry, from noble-butane having a low value in use, C4 oil can be achieved with high added value. In addition, it is possible to obtain an economical benefit by satisfying the demand of n-butene and 1,3-butadiene by securing a single production process capable of producing n-butene and 1,3-butadiene without installing a naphtha cracker, It has the advantage of being able to actively cope with market changes in the future.

1 is a graph showing the results of oxidative dehydrogenation of n-butane using carbon dioxide and oxygen as oxidizing agents on a magnesium orsorbanate catalyst according to Example 1 and Comparative Example 1 of the present invention during 6 hours, Lt; RTI ID = 0.0 > dehydrogenation < / RTI >
2 is a graph showing the results of the oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as oxidizing agents on a magnesium orsorbanate catalyst according to Example 1 and Comparative Example 1 of the present invention for 6 hours, The conversion of butane, the degree of selectivity of dehydrogenation products, and the yield of the dehydrogenation product.
3 is a graph showing the results of oxidative dehydrogenation of n-butane using carbon dioxide and oxygen as oxidizing agents on a magnesium orobarnadate catalyst according to Example 1 and Comparative Example 1 of the present invention for 6 hours, FIG. 5 is a graph showing the distribution of products of the dehydrogenation reaction product. FIG.
4 is a graph showing the results of the oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as oxidizing agents on a magnesium orsorbanate catalyst according to Example 2 of the present invention for 6 hours, , The selectivity of dehydrogenation products, and the activity difference with respect to the yield.
FIG. 5 is a graph showing the results of the oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as oxidizing agents on a magnesium orsorbanate catalyst according to Example 2 of the present invention for 6 hours and the distribution of dehydrogenation products FIG.

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

[ Manufacturing example  One]

Single step sol- Gel method  Magnesium by Orsobana Dating  catalyst( Mg ₃ ( VO ₄ ) ₂ - MgO -ZrO ₂  : Single stage sol-gel method)

To prepare a magnesium orthobarnadate catalyst having a magnesia: zirconia = 4: 1 molar ratio and a vanadium content of 5.6 wt% by 2.5 g of a single step sol-gel method, 8.2 g of magnesium nitrate and 1.8 g of zirconium oxynitrate 1.8 g was dissolved in distilled water (10 ml) to prepare a mixed precursor solution of magnesium and zirconium. At the same time, 7.6 g of citric acid was dissolved in distilled water (8 ml) to prepare a citric acid solution. The magnesium-zirconium mixed precursor solution and the citric acid solution were mixed to prepare a mixed citric acid precursor solution. Separately, 0.32 g of ammonium metavanadate and 0.27 g of citric acid were dissolved in distilled water (6 ml) to prepare a vanadium precursor solution. The mixed citric acid precursor solution and the vanadium precursor solution were mixed to prepare a catalyst-forming solution, and then the catalyst-forming solution was stirred while heating to 70 ° C. Thereafter, when the solution begins to swell as NO _x gas is generated in the catalyst-forming solution, the beaker containing the catalyst-forming solution is transferred to an oven and dried at 170 ° C. for about 12 hours to remove NO _x The gas was completely removed. As a result, a solid sponge type catalyst precursor was obtained. Then, the catalyst precursor was pulverized into a powder form and then heat-treated for 3 hours in an electric furnace in an air atmosphere at a temperature of 550 ° C. to obtain a magnesium orsorbanate catalyst (Mg ₃ ( VO ₄ ) ₂ -MgO-ZrO ₂ : single step sol-gel method).

[compare Manufacturing example  One]

Gel-oxalate < / RTI > To zirconia Supported  magnesium Orsobana Day Catalyst ( Mg ₃ ( VO ₄ ) ₂ / ZrO ₂ : Gel- Oxalate  And continuous Impregnation method )

To prepare 5 g of zirconia, 9.5 g of zirconium chloride was dissolved in ethanol (500 ml) to prepare a zirconium ethanol solution. At the same time, 12.3 g of oxalic acid dihydrate was dissolved in ethanol (100 ml) to prepare an oxalic acid ethanol solution. The two fully dissolved solutions were mixed using a syringe pump so that the oxalic acid ethanol solution was injected into the zirconium ethanol solution at a rate of 50 ml per hour, followed by stirring for about 3 hours. 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 process of filtering the ethanol solution in the phase-separated mixed solution to wash out unnecessary ions such as chloride and washing and stirring with ethanol solution 4 to 5 times with a centrifuge, and then drying the obtained solid sample at 80 ° C for 12 hours . The resulting solid samples were heat treated in an electric furnace in an air atmosphere at a temperature of 550 DEG C for 3 hours to prepare zirconia produced by the gel-oxalate method.

A magnesium orsorbanate catalyst supported on zirconia was prepared by supporting a magnesium salt and a vanadium salt on the prepared zirconia carrier so that the vanadium loading was 5.6 wt%. The specific manufacturing method is as follows. 1.1 g of magnesium nitrate hexahydrate was dissolved in a small amount of distilled water and mixed with 2.0 g of zirconia prepared by the method of Preparation Example 1 by the impregnation method. The magnesium-bearing zirconia sample was dried at 80 ° C. for 12 hours, and the resulting solid sample was heat-treated for 3 hours at 550 ° C. in an electric furnace in an air atmosphere to form a magnesium salt as a magnesia. 0.3 g of ammonium metavanadate (magnesium: vanadium atom ratio of 3: 2) was dissolved in a small amount of oxalic acid aqueous solution obtained by dissolving 0.7 g of oxalic acid in the obtained magnesia / zirconia sample, followed by impregnation with an aqueous ammonium metavanadate solution Dried at 80 DEG C for 12 hours to obtain a solid sample, and then subjected to heat treatment for 3 hours while maintaining the temperature at 550 DEG C in an electric furnace in an air atmosphere to prepare a magnesium orobarnadate catalyst supported on zirconia. The magnesium orobarnadate catalyst prepared through the above process was named Mg ₃ (VO ₄ ) ₂ / ZrO ₂ (gel-oxalate and continuous impregnation method).

[compare Manufacturing example  2]

Gel- By the oxalate method  Manufactured To zirconia  The magnesia / Zirconia Of the composite carrier  The magnesia / Zirconia On the composite carrier wall Ground magnesium Orsobana Dating  catalyst( Mg ₃ ( VO ₄ ) ₂ / MgO / ZrO ₂ : Gel- Oxalate  And two-stage impregnation)

To prepare 5 g of zirconia, 9.5 g of zirconium chloride was dissolved in ethanol (500 ml) to prepare a zirconium ethanol solution. At the same time, 12.3 g of oxalic acid dihydrate was dissolved in ethanol (100 ml) to prepare an oxalic acid ethanol solution. The two solutions sufficiently dissolved were introduced into the zirconium ethanol solution at a rate of 50 ml per hour by using a syringe pump, and the mixture was stirred for about 3 hours. The mixed solution was agitated at room temperature for 3 hours using a magnetic stirrer so that sufficient agitation was performed, and then left for 12 hours at room temperature for phase separation. The process of filtering the ethanol solution in the phase-separated mixed solution to wash out unnecessary ions such as chloride and washing and stirring with ethanol solution 4 to 5 times with a centrifuge, and then drying the obtained solid sample at 80 ° C for 12 hours . The resulting solid samples were heat treated in an electric furnace in an air atmosphere at a temperature of 550 DEG C for 3 hours to prepare zirconia produced by the gel-oxalate method.

A magnesium salt was supported on zirconia prepared by the above-described gel-oxalate method to prepare a magnesia / zirconia composite support at a magnesia: zirconia molar ratio of 4: 1. The specific manufacturing method is as follows. To prepare 3 g of the magnesia-zirconia composite carrier, 10.8 g of magnesium nitrate hexahydrate was dissolved in a small amount of distilled water, and each of the aqueous solutions was mixed with 1.3 g of the prepared zirconia by a general initial impregnation method . The magnesium-bearing zirconia sample was dried at 80 ° C. for 12 hours, and the resulting solid sample was heat-treated for 3 hours at 550 ° C. in an electric furnace in an air atmosphere to form a magnesium salt as a magnesia, .

To 1 g of the above-prepared magnesia / zirconia composite carrier, 0.14 g of ammonium metavanadate was dissolved in a small amount of oxalic acid solution in which 0.31 g of oxalic acid was dissolved and impregnated so that the supported amount of vanadium base was 5.6% by weight, followed by drying at 80 ° C for 12 hours, After obtaining a solid sample, a magnesium orsorbanadate catalyst supported on a magnesia / zirconia composite carrier was prepared by performing heat treatment for 3 hours while maintaining the temperature at 550 ° C in an electric furnace in an air atmosphere. The catalyst prepared by the above procedure was mixed with Mg ₃ (VO ₄ ) ₂ / MgO / ZrO ₂ (Gel-oxalate and two-stage impregnation method).

[compare Manufacturing example  3]

The magnesia- Zirconia Of the composite carrier  The magnesia- Zirconia On the composite carrier Supported  magnesium Orsobana Dating  Catalyst (Mg ₃ (VO ₄ ) ₂ / MgO-ZrO ₂ : Gel- Oxalate  And Impregnation method )

In order to prepare 5 g of magnesia-zirconia composite carrier having a magnesia: zirconia = 4: 1 molar ratio, 6.7 g of magnesium chloride and 4.1 g of zirconium chloride were dissolved in ethanol (500 ml), and a mixed ethanol solution of magnesium and zirconium , And at the same time, 26.6 g of oxalic acid dihydrate was dissolved in ethanol (200 ml) to prepare an oxalic acid ethanol solution. The sufficiently dissolved two solutions were mixed using a syringe pump so that the oxalic acid ethanol solution was injected into the mixed ethanol solution of magnesium and zirconium at a rate of 50 ml per hour, and the mixture was stirred sufficiently. The mixed solution was agitated 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 process of filtering the ethanol solution in the phase-separated mixed solution to wash out unnecessary ions such as chloride and washing and stirring with ethanol solution 4 to 5 times with a centrifuge, and then drying the obtained solid sample at 80 ° C for 12 hours . The resulting solid sample was heat-treated for 3 hours at an electric furnace in an air atmosphere at a temperature of 550 ° C to prepare a magnesia-zirconia composite carrier.

To 1 g of the prepared magnesia-zirconia composite carrier, 0.14 g of ammonium metavanadate was dissolved in a small amount of oxalic acid solution containing 0.31 g of oxalic acid dissolved therein and impregnated so as to have a vanadium base loading of 5.6% by weight, followed by drying at 80 ° C for 12 hours, After obtaining a solid sample, a magnesium orsorbanate catalyst supported on a magnesia-zirconia composite carrier was prepared by heat treatment for 3 hours while maintaining the temperature at 550 ° C in an electric furnace in an air atmosphere. The catalyst prepared by the above procedure was mixed with Mg ₃ (VO ₄ ) ₂ / MgO-ZrO ₂ (Gel-oxalate and impregnation method).

[compare Manufacturing example  4]

In the sol-gel method  The magnesia- Zirconia Of the composite carrier  The magnesia- Zirconia On the composite carrier Supported  Magnesium orthovanadate catalyst ( Mg ₃ ( VO ₄ ) ₂ / MgO - ZrO ₂  : Sol-gel method and Impregnation method )

To prepare a magnesia-zirconia composite carrier having a composition ratio of magnesia: zirconia = 4: 1 by a sol-gel method of 2.5 g, 9.1 g of magnesium nitrate and 2.1 g of zirconium oxynitrate were dissolved in distilled water (12 ml) Zirconium mixed precursor solution, and at the same time, 8.5 g of citric acid was dissolved in distilled water (9 ml) to prepare a citric acid solution. The precursor solution and the citric acid solution were mixed to prepare a carrier-forming solution, and the carrier-forming solution was stirred while being heated to 70 ° C. Since, NO which is when, while the NO _x gas generated in the carrier to form a solution the solution is started to climb swollen, by moving the beaker, wherein the carrier forms a solution contained in an oven dried for about 12 hours at 170 ℃ contained in the carrier to form a solution _x The gas was completely removed. As a result, a carrier precursor in the form of a solid sponge was obtained. Then, the carrier precursor was pulverized into a powder form and then heat-treated for 3 hours in an electric furnace in an air atmosphere at a temperature of 550 ° C to prepare a magnesia-zirconia composite carrier prepared by a sol-gel method.

To 1 g of the prepared magnesia-zirconia composite carrier, 0.14 g of ammonium metavanadate was dissolved in a small amount of oxalic acid solution containing 0.31 g of oxalic acid dissolved therein and impregnated so as to have a vanadium base loading of 5.6% by weight, followed by drying at 80 ° C for 12 hours, After obtaining a solid sample, a magnesium orsorbanate catalyst supported on a magnesia-zirconia composite carrier was prepared by heat treatment for 3 hours while maintaining the temperature at 550 ° C in an electric furnace in an air atmosphere. The catalyst prepared by the above procedure was mixed with Mg ₃ (VO ₄ ) ₂ / MgO-ZrO ₂ (Sol-gel method and impregnation method).

[ Example  One]

continuity Flow equation  Of n-butane using carbon dioxide and oxygen as oxidant through a catalytic reactor Oxidative  Dehydrogenation reaction

The oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as an oxidizing agent was carried out for 6 hours using the magnesium orobanadate catalyst prepared by the single step sol-gel method of Production Example 1, Respectively.

The reactant used in the oxidative dehydrogenation reaction of n-butane in this Example 1 is a C ₄ mixture containing 99.4% by weight of n-butane, the composition of which is shown in Table 1 below.

Composition of C ₄ mixture used as reactant Furtherance Molecular formula weight% i-butane C ₄ H ₁₀ 0.18 n-butane C ₄ H ₁₀ 99.40 1-butene C ₄ H ₈ 0.34 Cis-2-butene C ₄ H ₈ 0.08 Sum 100.00

As a reactant, the C4 mixture was injected in the form of a mixed gas with oxygen, carbon dioxide and nitrogen. The composition ratio of the reactants was set based on the amount of n-butane in the C4 mixture, and the ratio of n-butane: oxygen: carbon dioxide: nitrogen was set to be 4: 8: 28: 60.

The reaction is carried out in such a manner that the catalyst powder is immobilized in a linear quartz reactor for the catalytic reaction and the reaction is carried out while the reaction product is continuously passed through the catalyst layer in the reactor after the reactor is installed in the electric furnace and the reaction temperature of the catalyst layer is kept constant. Respectively.

The reaction rate was 55.5 ml · min ^-1 g _cat ^-1 based on n-butane. The temperature of the fixed-bed reactor was raised from room temperature to 560 ° C by flowing oxygen, carbon dioxide and nitrogen before flowing the reactants. The reaction temperature was maintained at 560 ° C And the reaction was carried out. The products after the reaction include n-butene and 1,3-butadiene, which are the main products of the present reaction, by-products such as carbon dioxide due to complete oxidation, by-products by cracking, by-products by isomerization, and n-butane Therefore, gas chromatography was used for separation and analysis.

Conversion and dehydrogenation reaction product selectivity of n-butane by oxidative dehydrogenation of n-butane using carbon dioxide and oxygen as oxidizing agents on a magnesium orobanadate catalyst prepared according to the single step sol-gel method of Preparation Example 1 The yields of dehydrogenation reaction products (n-butene and 1,3-butadiene) were calculated by the following equations (1), (2) and (3) And the results of the reaction at 6 hours after the reaction proceeded are shown in Table 3 and FIGS. 2 and 3.

[ Equation  One]

[ Equation  2]

[ Equation  3]

In the oxidative dehydrogenation reaction using carbon dioxide and oxygen as an oxidizing agent of the magnesium orobanadate catalyst prepared by the single step sol-gel method according to the method according to Production Example 1, catalyst Dehydrogenation reaction product yield (%) Time (h) One 2 3 4 5 6 Mg ₃ (VO ₄ ) ₂ -MgO-ZrO ₂
(Single step sol-gel method) 23.3 23.6 24.5 24.6 24.2 24.4

In the oxidative dehydrogenation reaction of the magnesium orsorbanate catalyst prepared by the single step sol-gel method according to the method of Production Example 1 using carbon dioxide and oxygen as the oxidizing agent, the catalytic activity at 6 hours after the reaction catalyst n-butane
Conversion Rate n-butene
Conversion Rate 1,3-BD
Selectivity C1 to C3
Selectivity CO
Selectivity CO ₂
Selectivity TDP *
yield Mg ₃ (VO ₄ ) ₂ -MgO-ZrO ₂
(Single step sol-gel method) 61.9 11.2 28.3 1.8 36.7 20.7 24.4
39.5

As shown in Tables 2 and 3 and FIGS. 1 to 3, in the case of the oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as an oxidizing agent, deactivation was not performed as in the case of using only oxygen as an oxidizing agent, Butadiene, and the selectivity of carbon dioxide was decreased. (In the oxidative dehydrogenation reaction of n-butane using only oxygen as the oxidizing agent, the selectivity of carbon dioxide Degree: 30-35%).

[ Comparative Example  One]

compare Manufacturing example  1 to 4, the gel- Oxalate  And Impregnation method , Sol-gel method  And By impregnation  The produced magnesium Orsobana Dating  Using the catalyst's carbon dioxide and oxygen as oxidizing agents Oxidative  Dehydrogenation reaction

For comparison with the activity results of the oxidative dehydrogenation using carbon dioxide and oxygen as the oxidizing agent through the magnesium orobarnadate catalyst obtained by the single step sol-gel method according to the method of Example 1 of the present invention, Oxalate prepared by the method according to Examples 1 to 4 and a magnesium orobarnadate catalyst prepared by the impregnation method, the sol-gel method, and the impregnation method were used, and carbon dioxide and oxygen were used as an oxidizing agent in the order of Example 1 An oxidative dehydrogenation reaction of n-butane was carried out.

The results of the reaction test according to Comparative Example 1 are shown in Tables 4 and 5 and Figs. 1 to 3, and the results shown in Table 4 and Fig. 1 show that the magnesium ores The oxidative dehydrogenation reaction using carbon dioxide and oxygen as an oxidizing agent through a soba or dating catalyst showed the reaction activity change over 6 hours as in Example 1. The results shown in Table 5 and Figs. 2 and 3 show that 6 hours . ≪ / RTI >

Oxidative dehydrogenation of the magnesium orsorbanate catalyst prepared by gel-oxalate, impregnation, sol-gel and impregnation methods according to the methods of Comparative Production Examples 1 to 4 was carried out for 6 hours in an oxidative dehydrogenation reaction using oxidizing agent Active trend catalyst Dehydrogenation reaction product yield (%) time
(h) One 2 3 4 5 6 Mg ₃ (VO ₄ ) ₂ / ZrO ₂
(Gel-oxalate and
Continuous impregnation method) 6.8 7.0 7.3 7.3 7.4 7.5 Mg ₃ (VO ₄ ) ₂ / MgO / ZrO ₂
(Gel-oxalate and
Two-step impregnation method) 18.7 19.1 18.6 18.0 19.0 18.3 Mg ₃ (VO ₄ ) ₂ / MgO-ZrO ₂
(Gel-oxalate and impregnation method) 20.6 20.4 20.7 20.0 20.1 20.2 Mg ₃ (VO ₄ ) ₂ / MgO-ZrO ₂
(Sol-gel method and impregnation method) 18.8 20.1 19.7 19.4 18.2 19.6

Oxidative dehydrogenation using carbon oxides and oxygen of magnesium oresorbadate prepared by gel-oxalate and impregnation method, sol-gel method and impregnation method according to the method according to Comparative Preparation Examples 1 to 4 was carried out for 6 hours The catalyst activity catalyst n-butane
Conversion Rate n-butene selectivity 1,3-BD
Selectivity C1-C3
Selectivity CO
Selectivity CO ₂
Selectivity TDP ^*
yield Mg ₃ (VO ₄ ) ₂ / ZrO ₂
(Gel-oxalate and
Continuous impregnation method) 49.2 9.2 6.0 1.9 57.3 24.9 7.5 15.2 Mg ₃ (VO ₄ ) ₂ / MgO / ZrO ₂
(Gel-oxalate and
Two-step impregnation method) 55.6 11.0 21.9 3.3 32.0 31.2 18.3 32.9 Mg ₃ (VO ₄ ) ₂ / MgO-ZrO ₂
(Gel-oxalate and
Impregnation method) 55.8 11.1 25.1 2.6 34.8 25.7 20.2 36.2 Mg ₃ (VO ₄ ) ₂ / MgO-ZrO ₂
(Sol-gel method and impregnation method) 58.1 10.3 23.4 3.1 35.6 26.9 19.6 33.7

[ Example  2]

Single step In the sol-gel method  The magnesium Orsobana Dating  catalyst( Mg ₃ ( VO ₄ ) ₂ -MgO-ZrO ₂  : Single step Sol-gel method ) Using carbon dioxide and oxygen as oxidizing agents Oxidative  Dehydrogenation reaction activity

The magnesium orobanadate catalyst prepared by the single step sol-gel method according to the production method of the present invention was oxidized in the same manner as in Example 1, except that the oxidizing agent of n-butane using carbon dioxide and oxygen as the oxidizing agent Dehydrogenation reaction was carried out. Specifically, the reaction was carried out at 500, 520, 540, 560, 580, 600 ° C. in the oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as the oxidizing agent, , Table 6 and FIG. 4 show the results of the reaction test according to Example 2, and the conversion of n-butane to the oxidative dehydrogenation reaction of n-butane, the degree of selectivity of dehydrogenation product, Yield. Table 6 and FIG. 5 also show the distribution of dehydrogenation products after 6 hours in the oxidative dehydrogenation reaction of n-butane.

In the oxidative dehydrogenation reaction of n-butane using oxidizing agent of carbon dioxide and oxygen in magnesium orsorbanate catalyst prepared by single step sol-gel method, Reaction temperature n-butane
Conversion Rate n-butene selectivity 1,3-BD
Selectivity C1-C3
Selectivity CO
Selectivity CO ₂
Selectivity TDP ^*
yield 500 ℃ 52.9 12.3 28.2 1.3 30.3 27.3 21.5 40.5 520 ℃ 56.0 11.7 28.5 1.4 33.8 24.1 22.5 40.2 540 DEG C 60.7 11.0 28.0 1.5 31.8 27.1 23.7 39.0 560 ° C 61.9 11.2 28.3 1.8 36.7 20.7 24.4 39.5 580 ° C 61.7 11.5 26.3 2.8 34.4 24.4 23.3 37.8 600 ℃ 65.0 10.2 23.5 4.8 35.6 24.8 21.9 33.7

As shown in Table 6 and FIG. 4, the conversion of n-butane, the degree of selectivity and yield of dehydrogenation products differed according to the reaction temperature, and the conversion rate tended to increase with increasing reaction temperature. The selectivity of dehydrogenation products tended to decrease continuously. The yield tended to increase with increasing temperature, and it was confirmed that the highest value was obtained at 560 ° C. The selectivity of specific dehydrogenation products is shown in Table 6 and FIG. 5. As a result, as the reaction temperature increases, the cracking reaction is promoted by heat, and the selectivity of C1 to C3 tends to increase. As a result, the total dehydrogenation product The selectivity of n-butene and 1,3-butadiene also tended to decrease, as shown in Fig. The selectivity of carbon monoxide, which is a major byproduct, tended to increase slightly within the error range as the reaction temperature increased, and the selectivity of carbon dioxide tended to decrease slightly within the error range. As a result, the conversion rate of n-butane increased and the degree of selectivity of dehydrogenation products (n-butene and 1,3-butadiene) decreased with increasing reaction temperature as a whole. The yield was present.

Claims (13)

A mixed gas containing n-butane, oxygen, carbon dioxide and nitrogen is used as a reactant on a magnesium orobarnadate catalyst prepared by a single-step sol-gel process, which comprises the steps of: Butane and 1,3-butadiene characterized in that the oxidative dehydrogenation reaction of n-butane used is carried out.
(a) dissolving a magnesium precursor and a zirconium precursor in a first solvent to prepare a mixed precursor solution of magnesium and zirconium;
(b) dissolving the solid acid in a second solvent to produce a solid acid solution;
(c) mixing the mixed precursor solution of magnesium and zirconium prepared in step (a) and the solid acid solution prepared in step (b) to prepare a mixed solid acid precursor solution;
(d) dissolving the vanadium precursor and the solid acid in a third solvent to prepare a vanadium precursor solution;
(e) mixing the mixed solid acid precursor solution prepared in step (c) and the vanadium precursor solution prepared in step (d) to prepare a catalyst-forming solution; And
(f) thermally drying the catalyst-forming solution to obtain a solid material, followed by heat treatment to obtain a magnesium orsorbanate catalyst.
2. The method of claim 1, further comprising the step of adding ethylene glycol to the catalyst-forming solution prepared in step (e) before step (f). -Butadiene.
The method of claim 1, wherein the magnesium precursor used in step (a) is at least one selected from a chloride precursor and a nitrate precursor of magnesium, and the zirconium precursor is a precursor of zirconium chloride, an oxynitrate precursor and an oxychloride precursor Butene and 1,3-butadiene. ≪ RTI ID = 0.0 > 1. < / RTI >
The method of claim 1, wherein the first solvent in step (a), the second solvent in step (b), and the third solvent in step (d) are selected from water or alcohol. Butene and 1,3-butadiene.
3. The method according to claim 1, wherein the solid acid in the step (b) and the step (d) is at least one selected from the group consisting of citric acid, succinic acid, malic acid and tartaric acid. Gt;
The method of claim 1, wherein the molar ratio of the solid acid: vanadium precursor used in step (d) is 0.5 to 2: 1.
3. The process according to claim 2, wherein the molar ratio of ethylene glycol to the total solid acid used in step (b) and step (d) in step (e ') is 0.5 to 4: , 3-butadiene.
The method according to claim 1, wherein the thermal drying in step (f) is performed in a temperature range of 40 to 200 ° C, and the heat treatment is performed in a temperature range of 400 to 1000 ° C. Butadiene.
The method of claim 1, wherein the vanadium content in the magnesium orobarnadate catalyst obtained in step (f) is 4.2 to 11.2 wt% based on the total weight of the catalyst. Gt;
The process for preparing n-butene and 1,3-butadiene according to claim 1, wherein the oxidative dehydrogenation reaction of n-butane using carbon dioxide and oxygen as an oxidizing agent is carried out at 300 to 800 ° C.
The method as claimed in claim 1, wherein the mixed gas has a volume ratio of normal-butane: oxygen: carbon dioxide: nitrogen of 2: 10: 0.5 to 30:20: 30: Butadiene.
The method of claim 1, wherein the mixed gas is injected at a weight hourly space velocity (WHSV) of 1 to 140 ml · min ^-1 g _cat ^-1 based on n-butane. Butene and 1,3-butadiene.



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