KR20140085776A - A catalyst for dehydrogenation and dehydroisomerization of n-butane and a method for producing a mixture of n-butane, 1,3-butadiene and iso-butene in high yield using the same - Google Patents

Abstract

The present invention relates to a catalyst for dehydrogenation and dehydroisomerization of n-butane, and a method for manufacturing a mixture of n-butane, 1,3-butadiene and iso-butane by dehydrogenation and dehydroisomerization of n-butane using the same and, more specifically, to a catalyst which is modified by adding cesium to a chlorinated raw catalyst in which a gamma alumina carrier is supported on platinum and tin, and to a method for manufacturing a mixture of n-butane, 1,3-butadiene and iso-butane in a high yield by dehydrogenation and dehydroisomerization of n-butane by using the same.

Description

The present invention relates to a catalyst for dehydrogenation and dehydrogenation isomerization of n-butane and a method for producing a mixture of n-butene, 1,3-butadiene and isobutene in high yield by using the catalyst for dehydrogenation and dehydroisomerization of n-butane and a method for producing a mixture of n-butane, 1,3-butadiene and iso-butene in high yield using the same}

The present invention relates to a catalyst for the dehydrogenation and dehydrogenation isomerization of n-butane and a process for preparing a mixture of n-butene, 1,3-butadiene and isobutene by dehydrogenation and dehydrogenation isomerization of n-butane using the same , More particularly, to a catalyst prepared by modifying cesium (Cs) to a chlorosilicate raw catalyst supported on platinum and tin components in a gamma alumina carrier, and a dehydrogenation and dehydrogenation reaction of n-butane using this catalyst Butene, 1,3-butadiene and isobutene in a high yield.

In recent years, the supply of light olefins, which are raw materials for various petrochemical products, has become a concern of the market due to the surge in olefin prices in the petrochemical market. Butenes, 1,3-butadiene, and isobutene, which are raw materials for various synthetic rubber and copolymer products, are also in the light olefins whose demand and value are increasing mainly in China, and methods for obtaining them include naphtha cracking, Dehydrogenation reaction of n-butane or n-butene, and dehydrogenation of isobutane. Of these, about 90% or more of n-butene, 1,3-butadiene and isobutene supplied to the market are supplied by the naphtha cracking process. In this situation, the operation of the naphtha cracking process has a great impact on the market .

However, the naphtha cracking process is not a sole process for producing noble-butene, 1,3-butadiene, and isobutene due to the characteristics of processes for producing basic oils such as ethylene and propylene, , Naphtha crackers can not be newly added or expanded in order to expand production of 3-butadiene and isobutene, and even if naphtha crackers are added, other basic oils other than n-butene, 1,3-butadiene and isobutene are produced in surplus . In addition, recent trends in the establishment and operation of naphtha cracking processes are in the direction of higher yields as the demand for ethylene and propylene is greatly increased, and the yield of noble-butene, 1,3-butadiene and isobutene , But the process has been changed to a process using light hydrocarbons such as ethane and propane, which have a high yield relative to other basic oils such as ethylene and propylene, as raw materials. In addition, since the naphtha raw material that can obtain noble-butene, 1,3-butadiene, and isobutene oil is continuously increased in price, and the ratio of naphtha cracking process is relatively reduced accordingly, It is becoming increasingly difficult to secure a mixture of n-butene, 1,3-butadiene and isobutene, i.e., n-butene, 1,3-butadiene and isobutene through the naphtha cracking process.

As such, the naphtha cracking process accounts for most of the mixture of n-butene, 1,3-butadiene and isobutene, but it can not be an effective alternative to solve the supply-demand imbalance caused by recent increases in demand It is true. For this reason, the reaction of obtaining n-butene and 1,3-butadiene by dehydrogenation to remove hydrogen from n-butane or n-butene or obtaining isobutene by dehydrogenation of isobutane is a recent reaction of n-butene , 1,3-butadiene, and isobutene.

Normal-to catalysts used in the dehydrogenation process of butane and isobutane is mainly alumina (Al ₂ O ₃₎ to the carrying platinum (Pt) and tin (Sn) catalyst to the carrier, chromia (Cr ₂ O ₃ ) as a main component are known.

Representative processes using chromia-alumina-based catalysts include Houdry process for producing n-butene from n-butane, and process for producing 1,3-butadiene from n-butane, UCI-ABB Lummus Crest's CatadieneTM process.

The dehydrogenation process using platinum (Pt) as the main catalyst component was developed from the end of the 1960s and was able to continuously operate the noble metal catalyst device in the early 1970s without shutting down the process unit for a long time The Oleflex process of UOP, a dehydrogenation process, has been developed but is now being applied to the production of propylene and isobutylene.

Conventionally, a catalyst mainly composed of platinum and tin is generally used as a carrier, and gamma (?) Crystalline alumina (Al ₂ O ₃ ) having a nitrogen adsorption specific surface area of 150 m ² / g or more and a high purity of 99.9% And further using an alkali metal or an alkaline earth metal to adjust the acid point of the catalyst is known.

Gamma (γ) crystalline alumina itself has a strong acid point, which is likely to cause side reactions. The strong acid sites cause cracking of the hydrocarbons, which reduces the olefin selectivity of the dehydrogenation reaction or causes the deposition of hydrocarbons (caulking) Resulting in loss of the hydrocarbon component as a raw material and lowering of the yield of olefin.

For this reason, in the dehydrogenation process of an alkane, a catalyst prepared by neutralizing or adjusting a acid site by adding an alkali metal or an alkaline earth metal is generally used in order to minimize side reactions caused by the acid sites of the catalyst support. US Pat. No. 4,677,237 discloses a catalyst Catalyst technology has been introduced that improves performance by supporting alkaline alkali metal on alumina to prevent shrinkage.

U.S. Pat. No. 4,886,928 discloses a process for the preparation of a catalyst for the catalytic dehydrogenation of a C2-C5 normal paraffin or isoparaffin containing platinum, tin, yttrium, an alkali metal or an alkaline earth metal in a dehydrogenation reaction with chlorine (Cl) Lt; / RTI > catalyst.

U.S. Patent No. 5,151,401 discloses a method in which chlorine is sufficiently removed through a separate washing process after firing in a catalyst containing zinc aluminate (ZnAl ₂ O ₄ ) as a carrier and platinum and tin as main components, And a method for producing the catalyst so that the content is 0.05 wt% or less.

Thus, the conventional alkane dehydrogenation catalyst intentionally removes chlorine (Cl) through the final calcining process of the catalyst or a separate washing or steaming treatment, and even if there is residual chlorine unavoidably, Is minimized and used.

On the other hand, the naphtha reforming process is a process for converting n-paraffins and naphthenes into aromatic hydrocarbons, and the acid function is essential for the production of aromatic compounds. For this reason, in the naphtha-reforming process, catalysts of the type including one or more other metals and platinum deposited on a chlorinated aluminum oxide carrier have been known for a long time.

That is, unlike the dehydrogenation process of normal paraffin, which has a negative effect on acid sites, acid sites play an important role in the naphtha reforming process, so the carrier is chlorinated rather than neutral or alkali-treated carriers and gamma alumina do. In addition, in order to maintain the acidic function of the catalyst in the process, a chlorine compound is continuously supplied to the system to supplement the acidic function.

In the naphtha-reforming process carried out on such a catalyst, a carbon-containing complex is generated by side reaction in the continuous contact process of the catalyst with the raw material simultaneously with the chemical conversion reaction of the paraffin and naphthenic hydrocarbon compound into the aromatic compound, . Such a carbonaceous complex or coke plugs the catalytically active site and interferes with the access of the reactant, and becomes a factor of inactivation of the catalyst. For this reason, on an industrial scale, after a period of hydrocarbon conversion reactions, the coke must be removed. This is done through the catalyst regeneration process. During the total period of use of the catalyst, the catalyst undergoes several regeneration steps until the catalyst becomes no longer usable and is replaced. This regeneration process generally involves the removal of coke deposited on the catalyst by burning, the drying of water produced in the combustion process, and the re-dispersion of the platinum (Pt) component sintered in the course of the reaction and coke combustion. And an oxychlorination step carried out in the presence of an oxidizing agent.

When the catalyst in the naphtha-reforming process is repeatedly cycled through such a reaction-regeneration step, a change in the structural characteristics such as a reduction in the surface area of alumina occurs largely, which in turn affects the naphtha-reforming reaction, Which is directly related to the lowering of the lifetime. For example, a reduction in surface area can cause sintering and coagulation of the finely dispersed active components, rendering catalyst activity itself impossible.

As described above, even though the dehydrogenation catalyst and the naphtha-reforming catalyst have a common feature that platinum and tin are the main components, the required catalyst characteristics are different and the reaction conditions are different. While the dehydrogenation process benefits from low pressures for high conversion rates, the naphtha reforming process is typically carried out under high pressure conditions, and additionally chlorine is added continuously to maintain the acid point function.

In addition, in the case of the naphtha-reforming catalyst, periodic regeneration process is required due to the precipitated coke in the reaction process. In this process, the structural change due to deterioration and thus the reduction of the specific surface area of the carrier are caused. Thus, over time, naphtha-reforming catalysts exhibit physical properties that differ from those at the initial point of time when they were loaded into the reactor.

Separately, the conversion of n-butene to isobutene is an isomerization reaction in which a part of the bond forming the backbone of the molecule is rearranged and rearranged, so-called skeletal isomerization. The skeleton isomerization of n-butene to isobutene requires that the activated n-butene is reacted with skeleton isomerization through a single-molecule reaction mechanism at the acid site, so that the isobutene production rate is increased and the n-butene is activated at the B- (J. Korean Ind. Eng. Chem., Vol. 15, No. 6, 581-593 (2004)). Therefore, in the isomerization reaction of n-butene to isobutene, the strength, kind and concentration of acid sites are important factors affecting selectivity and yield.

In the process of studying a catalyst capable of converting n-butane to a mixture of n-butene, 1,3-butadiene and isobutene, the present inventors have found that the naphtha-reforming catalyst aged through repeated reaction- The fact that heat treatment under reducing atmosphere at specific temperature conditions after combustion removal, moisture drying and oxychlorination treatment can produce a high conversion and selectivity of n-butene, 1,3-butadiene and isobutene mixture (Korean Patent Application No. 10-2012-0080194).

However, the catalyst of the patent application of the present invention still contains a large amount of C1-C3 by-products due to side reactions such as cracking and the products of dehydrogenation and dehydrogenation isomerization of carbon number 4, namely, n-butene, The selectivity to the mixture was low, and the deactivation rate was fast. Thus, there was room for improvement of the catalyst performance.

Accordingly, the inventors of the present invention have found that, in order to overcome the limitations of the prior patent application filed by the inventors of the present invention [Korean Patent Application No. 10-2012-0080194], the present inventors suppressed side reactions in dehydrogenation and dehydrogenation reaction of n-butane Butanone, 1,3-butadiene, and isobutene, and developed a catalyst capable of increasing the selectivity to n-butene, 1,3-butadiene and isobutene.

According to the present invention, a catalyst having characteristics of a catalyst aged gradually over time by repeated cycles of reaction-regeneration of a naphtha-reforming catalyst containing platinum and tin as a main component is subjected to coke combustion removal, moisture drying and oxychlorination Butene, 1,3-butadiene and isobutene mixture while suppressing the side reaction in dehydrogenation and dehydrogenation isomerization of n-butane and modifying the addition of cesium component at a point in time after passing through the catalyst, It is possible to increase the selectivity, to produce the compound at a high yield, and to solve the problem that the inactivation problem is greatly improved.

Accordingly, an object of the present invention is to provide a process for producing a mixture of n-butene, 1,3-butadiene and isobutene, which comprises simultaneous dehydrogenation reaction of n-butane and dehydrogenation isomerization using n-butane as a raw material, (PtSn / γ-Al ₂ O ₃ -Cl) aged through repeated reaction-regeneration processes in the naphtha-reforming reaction so as to be able to generate the catalyst and the catalyst, Butene, 1,3-butadiene and isobutene in a high yield by dehydrogenation of n-butane and isomerization of dehydrogen using a catalyst.

The catalyst used in the dehydrogenation reaction and the dehydrogenation isomerization reaction of n-butane according to the present invention is characterized in that platinum and tin are supported on a carrier, the catalyst is chlorinated to contain excess chlorine, and platinum 0.1 Wherein the weight ratio of chlorine to platinum is from 1: 3 to 10: 1, the specific surface area of the catalyst is from 100 to 180 m ² / g, And further adding a cesium component to the feedstock catalyst in the range of 0.5 to 3.0 wt% based on the total weight of the catalyst before introduction of the cesium component.

In the present invention, the catalyst to be subjected to the reforming treatment by cesium addition is not particularly limited as long as it has the above-mentioned composition and characteristics, and for example, a platinum- A naphtha-reforming regenerated catalyst in which a tin catalyst has been treated with a conventional catalyst regeneration treatment process consisting of a coke combustion removal, a water drying and an oxychlorination treatment may be used, or a separately prepared catalyst may be used have.

Typical methods for preparing such naphthafluoroforming catalysts include, for example, the methods described in the examples of Korean Patent No. 10-0569853 and the methods of Examples of Korean Patent No. 10-0736189. Specifically, according to Example 1 of Korean Patent No. 10-0569853, tin chloride (tin chloride) and aqueous hydrochloric acid solution were added to gamma alumina having a specific surface area of 210 m ² / g, followed by dehydration after contacting for 3 hours, Subsequently, a hexachloroplatinic acid aqueous solution of a platinum compound is brought into contact. Thereafter, the catalyst is dried at 120 ° C. for 1 hour and then calcined at 500 ° C. for 2 hours to obtain a platinum / tin naphtha reforming catalyst (PtSn / γ-Al ₂ O ₃ ). According to Example 1 of Korean Patent No. 10-0736189, a tin chloride aqueous solution is added to 100 g of gamma alumina having a specific surface area of 200 m ² / g in the presence of hydrochloric acid and nitric acid, and the mixture is contacted for 3 hours, Dried at 120 ° C and then calcined at 500 ° C for 2 hours under air circulation. Subsequently, this solid was contacted with an aqueous solution of hexachloroplatinic acid, dried at 120 ° C for 1 hour, and then calcined at 500 ° C for 2 hours under air flow. The catalyst is then reduced at 500 캜 for 4 hours under a hydrogen flow to obtain a platinum / tin naphtha reforming catalyst (PtSn / γ-Al ₂ O ₃ ).

In the catalyst of the present invention, gamma-alumina can be used as a carrier as an example, and it is a carrier component most commonly used for industrially supporting highly dispersed noble metal components, And a specific surface area of 250 m ² / g can be used.

In the catalyst of the present invention, the platinum is used as a main metal serving as a catalytic active site, and the content of the platinum in the catalyst is preferably 0.1 to 1.0 wt%. If less than 0.1 wt% The conversion rate may be lowered. If the content is more than 1.0% by weight, the degree of dispersion of platinum is lowered and utilization of platinum, which is a high-priced noble metal, may be lowered.

In the catalyst of the present invention, the tin is used as an auxiliary metal to serve as a cocatalyst. If the content of tin is less than 0.1 wt%, the desired tin can not be expected to act as a cocatalyst, , The activity may be lowered by reducing the platinum active site, which is undesirable.

In the catalyst of the present invention, it is preferable that the content of chlorine is 0.5 to 3.0 wt%. If the amount of chlorine is less than 0.5 wt%, it is not possible to provide an appropriate acid point and dehydroisomerization of n-butane can not proceed properly. If the content is more than 10 wt%, the activity of the catalyst may be lowered due to poisoning of the noble metal by chlorine, which is not preferable.

In the catalyst of the present invention, it is preferable that the weight ratio of chlorine to platinum is in the range of 1: 3 to 10: 1. If the ratio is outside the above range, the balance between the metal function and the acid point function is broken, Or excessive acid sites may increase the side reaction or poisoning of the noble metal by chlorine may lower the activity of the catalyst.

The specific surface area of the catalyst of the present invention is preferably 100 to 180 m ² / g. If the amount of the catalyst is outside the above range, sintering and coagulation of the finely dispersed active components may be caused, not.

If the amount of cesium introduced into the catalyst of the present invention is less than 0.5% by weight based on the total weight of the catalyst before introduction of the cesium component, the effect of improving the selectivity of desired reaction products and the effect of damping of inactivation can not be expected. , The activity may be lowered to cause a sudden deactivation, which is undesirable.

In the catalyst of the present invention, there is no particular limitation on the introduction method of the introduced cesium, and the cesium precursor compound solution is impregnated with a catalyst, for example, a PtSn / γ-Al ₂ O ₃ -Cl catalyst, ≪ / RTI >

In the catalyst according to the present invention, the cesium precursor compound may be any conventional cesium compound, such as nitrate, sulfate, carbonate, hydroxide, chloride and the like, without limitation, for example, cesium nitrate (CsNO ₃ ), it is not preferable to use such as cesium carbonate (cesium carbonate, Cs ₂ CO _3), cesium chloride (cesium chloride, CsCl), cesium hydroxide (cesium hydroxide, CsOH), however, limited to this.

The reason why the solution of the cesium precursor compound is impregnated in the catalyst and then dried is to remove moisture after impregnating the cesium compound. The drying temperature and the drying time can be limited according to general moisture drying conditions. For example, Can be set at 50 to 200 ° C, preferably 80 to 150 ° C, and the drying time is 3 to 48 hours, preferably 6 to 24 hours.

After the drying, the heat treatment is a step of impregnating the cesium precursor compound to remove moisture through drying, and then decomposing and removing the salt in the cesium compound. The heat treatment is performed at a temperature of 200 to 700 ° C , 1 to 24 hours, preferably 300 to 600 ° C, for 2 to 12 hours. If the heat treatment temperature is less than 300 ° C., the effect of heat treatment may be insufficient. If the heat treatment temperature is higher than 700 ° C., the activity may be reduced due to grain growth due to sintering of platinum or formation of an excessive alloy between metals.

In addition, the catalyst of the present invention may be subjected to a reduction treatment suitable for manifesting the performance in the dehydrogenation and dehydrogenation isomerization of n-butane, which may be carried out in an actual process or may be carried out in advance through a reduction process. The catalyst of the present invention flows hydrogen gas mixed with pure hydrogen or nitrogen at a gas hourly space velocity (GHSV) of 0 to 2,000 cc / hr / g.cat, and is reduced at 400 to 700 ° C for 0.1 to 24 hours , It is possible to express sufficient activity.

The process for preparing a mixture of n-butene, 1,3-butadiene and isobutene by dehydrogenation and dehydrogenation isomerization of n-butane according to the present invention is characterized in that n-butane is used as a raw material To carry out dehydrogenation and dehydrogenation isomerization.

In the process for preparing a mixture of n-butene, 1,3-butadiene and isobutene by dehydrogenation and dehydrogenation isomerization of n-butane according to the present invention, the temperature of the dehydrogenation and dehydrogenation isomerization is 400 to 700 ° C , Preferably 500 to 700 ° C, and more preferably 450 to 600 ° C, and the pressure is preferably 0 to 10 atm, preferably 0.01 to 5 atm, and the normal-butane space velocity (GHSV) hr ^-1, and preferably is the 100 ~ 5000hr ^-1, the reaction conditions are not being used properly, the catalyst is used effectively in terms of the reactions do not occur sufficiently catalyst is out of the range, or may be less economical, additional troops It is possible to increase the cost due to the apparatus and to inconvenience to the operation (operation), and in some cases, to increase the unwanted side reaction on the catalyst or to promote the deactivation, By the input unnecessarily excessive undesirable can lead to increased operating cost of the separation of the recycled raw material.

In the dehydrogenation and dehydrogenation isomerization, hydrogen may be further added to the normal-butane stream, and the molar ratio of hydrogen to 1 mole of n-butane may be 0.1 to 100 moles, preferably 1 to 10 moles. The hydrogen acts to remove carbon deposits formed on the surface of the catalyst, for example, coke.

In the dehydrogenation and dehydrogenation isomerization reaction, if necessary, a diluent such as nitrogen, an inert gas or steam may be mixed in addition to the normal-butane.

According to the present invention, when the naphtha-reforming catalyst is gradually aged and the catalyst characteristics are changed as a result of exposure to the reaction-regeneration process repeated in the conversion reaction of paraffin and naphthene into aromatics, The present invention provides a method which can be usefully used in a reaction for converting a regenerated catalyst having physical properties into a dehydrogenation derivative of n-butane different from its intended use.

Since the dehydrogenation and dehydrogenation isomerization of n-butane using the catalyst according to the present invention exhibits high activity and selectivity in the conversion reaction into a high-value product having a high utilization value of n-butane, -Butadiene < / RTI > and isobutene, and exhibit improved long-term stability through inactivation relaxation.

FIG. 1 is a graph showing changes in reaction activity over time of dehydrogenation and dehydrogenation isomerization of n-butane over 6 catalysts according to Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention, A graph showing the difference.
2 is a graph showing the relationship between the reaction products of normal-butane dehydrogenation and dehydrogenation isomerization of n-butene, 1,3-butadiene and isobutene on the six catalysts of Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention Of the total yield and the difference of the total yield with time.

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

< Manufacturing example - Analysis of raw catalysts>

A process for producing a conventional naphtha-reforming catalyst, that is, impregnation of gamma alumina with tin, followed by calcination at 500 DEG C, then calcination at 500 DEG C with platinum supported thereon, reduction at 500 DEG C / Tin system naphtha reforming catalyst is used in a naphtha reforming process, the catalyst whose performance has been reduced by the coke is regenerated through coke combustion-water-drying-oxychlorination treatment by a conventional regeneration treatment method, The results of analyzing the characteristics of the regenerated catalyst (PtSn / Al ₂ O ₃ -Cl), which was repeated several times after the regeneration process, are shown in Table 1 below.

The catalysts having the compositions and characteristics of Table 1 were used in the following Examples 1 to 4 and Comparative Examples 1 and 2.

Example  One

A modified catalyst was prepared by adding cesium to the raw material catalyst (PtSn / Al ₂ O ₃ -Cl) so that the amount of cesium was 0.5 wt%. Specifically, 73.3 mg of cesium nitrate (CsNO ₃ ) was dissolved in distilled water (7.5 mL), and then this solution was impregnated with 10 g of the raw material catalyst (PtSn / Al ₂ O ₃ -Cl) and dried at 110 ° C for 8 hours. Thereafter, heat treatment was carried out under conditions of a dry air space velocity of 1500 hr &lt; ^-1 &gt; and an air flow at 550 DEG C for 3 hours. This catalyst was named PtSnCs (0.5). 2 g of the catalyst PtSnCs (0.5) thus heat-treated was charged into the reactor, and the catalyst was reduced at 570 ° C for 2 hours while flowing a mixed gas of 20 cc of pure hydrogen and 20 cc of nitrogen.

Thereafter, the dehydrogenation reaction was carried out by introducing nitrogen and n-butane mixed gas. At this time, the gas-space velocity (GHSV) of the normal-butane was 600 hr ^-1 , the mixing volume ratio of nitrogen and n-butane was 1: 1, the reaction temperature of the catalyst layer was maintained at 550 ° C. at normal pressure, Was analyzed by gas analysis GC connected to the reaction apparatus. From this, the conversion of n-butane and the selectivity of each reaction product were measured and are shown in Table 2 below.

The conversion of n-butane, selectivity and yield of each reactant were calculated by the following equations (1), (2) and (3).

[Equation 1]

&Quot; (2) &quot;

&Quot; (3) &quot;

Comparative Example  One

₂ g of the raw material catalyst (PtSn / Al ₂ O ₃ -Cl) was heat-treated at 550 ° C for 3 hours under a condition of air space velocity of 1500 hr ^-1 under air flow without addition of cesium. This catalyst was named PtSnCs (0.0). The catalyst was charged into a reactor and the catalyst was reduced at 570 캜 for 2 hours while flowing a mixed gas of 20 cc of pure hydrogen and 20 cc of nitrogen. Then, the dehydrogenation reaction was carried out by introducing nitrogen and n-butane mixed gas. At this time, the gas-space velocity (GHSV) of the normal-butane was 600 hr ^-1 , the mixing volume ratio of nitrogen and n-butane was 1: 1, the reaction temperature of the catalyst layer was maintained at 550 ° C. at normal pressure, Was analyzed by gas analysis GC connected to the reaction apparatus. From this, the conversion of n-butane and the selectivity of each reaction product were measured and are shown in Table 2 below.

Comparative Example  2

The procedure of Example 1 was repeated except that the amount of cesium introduced into the raw material catalyst was changed to 0.3 wt%. This catalyst was named PtSnCs (0.3). The composition of the gas produced by the reaction was analyzed by GC for gas analysis connected to the reaction apparatus. From this, the conversion of n-butane and the selectivity of each reaction product were measured and are shown in Table 2 below.

Example  2

The procedure of Example 1 was repeated except that the amount of cesium introduced into the raw material catalyst was changed to 0.7 wt%. This catalyst was named PtSnCs (0.7). The composition of the gas produced by the reaction was analyzed by GC for gas analysis connected to the reaction apparatus. From this, the conversion of n-butane and the selectivity of each reaction product were measured and are shown in Table 2 below.

Example  3

The procedure of Example 1 was repeated except that the amount of cesium introduced into the raw material catalyst was changed to 1.0 wt%. This catalyst was named PtSnCs (1.0). The composition of the gas produced by the reaction was analyzed by GC for gas analysis connected to the reaction apparatus. From this, the conversion of n-butane and the selectivity of each reaction product were measured and are shown in Table 2 below.

Example  4

The procedure of Example 1 was repeated except that the amount of cesium introduced into the raw material catalyst was changed to 2.0 wt%. This catalyst was named PtSnCs (2.0). The composition of the gas produced by the reaction was analyzed by GC for gas analysis connected to the reaction apparatus. From this, the conversion of n-butane and the selectivity of each reaction product were measured and are shown in Table 2 below.

Note 1) Selectivity for n-butene, 1,3-butadiene and isobutene, products of dehydrogenation and dehydrogenation reaction of n-butane.

2) Total yields of n-butene, 1,3-butadiene and isobutene, products of dehydrogenation and dehydrogenation isomerization of n-butane

As can be seen from Table 2 and FIG. 1, the PtSnCs (0.3) catalyst of Comparative Example 2 in which the amount of cesium added was 0.3 wt% as compared with Comparative Example 1 improved the selectivity, but the conversion decreased and consequently the yield decreased Can be seen. Also, the inactivation was not improved. In addition, the selectivity to n-butene, 1,3-butadiene and isobutene was greatly improved in Examples 1 and 2, and the yield after one hour of the initiation of the reaction was improved. As shown in Fig. 2, The yield is kept high as a whole.

Further, as shown in Table 2 and FIG. 1, the conversion ratio was improved in Examples 3 and 4, and the selectivity to n-butene, 1,3-butadiene and isobutene was greatly improved. As a result, Can be seen.

2, it can be seen that the yields in Examples 3 and 4 were significantly higher than those of Comparative Example 1 during the course of the reaction. In FIG. 1, the catalysts of Examples 3 and 4 were inactivated The rate was remarkably slowed and the decrease in activity was slower than that of the catalyst of Comparative Example 1, indicating that the reaction stability of the catalyst was greatly improved.

Claims (8)

A catalyst comprising platinum and tin supported on a support, the catalyst comprising 0.1 to 1.0 wt% of platinum, 0.1 to 2.0 wt% of tin and 0.5 to 3.0 wt% of chlorine based on the total weight of the catalyst, wherein the weight ratio of chlorine to platinum is (Cs) in an amount of 0.5 to 3.0% by weight is added to a raw material catalyst having a specific surface area of 100 to 180 m ² / g of platinum: chlorine = 1: 3 to 10, And a catalyst for dehydrogenation isomerization. The method according to claim 1,
The catalyst for dehydrogenation and dehydrogenation isomerization of n-butane is characterized in that the raw material catalyst is a regenerated catalyst that is used in a naphtha-reforming process and has undergone a regeneration treatment comprising coke removal, moisture drying and oxychlorination. The method according to claim 1,
The catalyst for dehydrogenation and dehydrogenation isomerization of n-butane is characterized in that the cesium-containing modification is carried out by impregnating a solution of cesium salt in water with a catalyst, followed by drying and heat treatment. The method of claim 3,
Wherein the cesium salt is cesium nitrate (CsNO ₃ ). The catalyst for dehydrogenation and dehydrogenation isomerization of n-butane. The method of claim 3, wherein the drying and heat treatment is performed by drying at 50-200 ° C for 3 to 48 hours and heat treatment at 200 to 700 ° C for 1 to 24 hours. The dehydrogenation and dehydrogenation of n-butane Catalyst for reaction. A process for producing n-butene, 1,3-propanediol, 1,3-butylene norbornene, and n-butene, characterized in that dehydrogenation and dehydrogenation isomerization are carried out using the catalyst according to any one of claims 1 to 5, A process for preparing a mixture of butadiene and isobutene. The method according to claim 6,
Wherein the dehydrogenation and dehydrogenation isomerization is carried out at a temperature of 400 to 700 ° C., 0 to 10 atm and a normal-butane space velocity of 50 to 5000 hr ^-1 . &Lt; / RTI &gt; The method according to claim 6,
Butane stream is further added with hydrogen in the dehydrogenation and dehydrogenation isomerization and the molar ratio of hydrogen to 1 mole of n-butane is from 0.1 to 100 moles, wherein n-butene, 1,3-butadiene and Gt; isobutene &lt; / RTI &gt;

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