KR20170077959A - Process for preparing propylene or butane from propane, butane or butadiene using hydrogen acceptor for dehydrogenation - Google Patents

Process for preparing propylene or butane from propane, butane or butadiene using hydrogen acceptor for dehydrogenation Download PDF

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KR20170077959A
KR20170077959A KR1020150187913A KR20150187913A KR20170077959A KR 20170077959 A KR20170077959 A KR 20170077959A KR 1020150187913 A KR1020150187913 A KR 1020150187913A KR 20150187913 A KR20150187913 A KR 20150187913A KR 20170077959 A KR20170077959 A KR 20170077959A
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propane
butane
butadiene
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KR101788270B1 (en
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고형림
정재원
이학범
김수영
최이선
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한경대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/12—Alkadienes
    • C07C11/16—Alkadienes with four carbon atoms
    • C07C11/167—1, 3-Butadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

Disclosed is a process for the production of propylene, butene or butadiene from propane or butane using a hydrogen acceptor for dehydrogenation reaction, wherein the conversion of propane or butane to propylene, butene or butadiene is excellent in conversion, selectivity of reaction and energy efficiency. The process for producing propylene, butene or butadiene from the above propane or butane comprises the steps of: (a) adding a catalyst layer comprising platinum, chromium, vanadia and a mixture thereof (content: 0.1 to 5 parts by weight per 100 parts by weight of the support) (Content: 0.5 to 40 parts by weight, relative to 100 parts by weight of the carrier) of a dehydrogenation catalyst and a dehydrogenation catalyst in which a main metal selected from the group is supported on a carrier; (b) continuing the oxidative-dehydrogenation reaction while continuously passing propane or butane through the catalyst bed of the reactor; (c) obtaining propylene, butene or butadiene, wherein the hydrogen acceptor reacts hydrogen produced by the dehydrogenation reaction with its lattice oxygen to produce water.

Description

Technical Field [0001] The present invention relates to a process for preparing propylene, butene or butadiene from propane or butane using a hydrogen acceptor for dehydrogenation reaction,

The present invention relates to a process for the production of propylene, butene or butadiene from propane or butane using a hydrogen acceptor for dehydrogenation reaction, and more particularly to a process for the production of propylene, butene or butadiene from propane or butane, Butene or butadiene from propane or butane using a hydrogen receptor for dehydrogenation reaction having excellent efficiency.

Generally, in the case of hydrocarbon gases, especially propane and butane, a process for producing propylene, butene or butadiene from propane or butane using a noble metal such as platinum or an oxide-based dehydrogenation catalyst such as chromium has been widely used industrially . However, since the dehydrogenation reaction of propane and butane is an endothermic reaction, the reaction temperature of the adiabatic reaction apparatus decreases with the progress of the reaction. Therefore, in order to increase the production amount of propylene, butene and butadiene, additional reaction heat must be supplied constantly. Also, the propane and butane dehydrogenation reaction is difficult to obtain a high conversion rate because the dehydrogenation reaction is an equilibrium reaction by the reversible reaction in which the yield of the maximum propylene, butene or butadiene is thermodynamically limited. Therefore, when heat generated by the oxidation reaction is added by simultaneously adding propane or butane and an oxidizing agent, the amount of heat supplied relative to the dehydrogenation reaction can be reduced, and hydrogen generated in the dehydrogenation reaction can be selectively oxidized It has heretofore been proposed to combine a process with a dehydrogenation process.

In general, O 2 , CO, CO 2 , N 2 O, steam, and sulfur compounds are used as the oxidizing agents used in oxidative dehydrogenation. Especially, O 2 , CO 2 and steam have been studied. Among them, oxygen having high oxidizing power has not been environmental hazard of oxygen itself, and since it exhibits high activity, many studies have been made on oxidative dehydrogenation technology using oxygen. However, when oxygen is used as the oxidizing agent, it has the disadvantage of lowering the selectivity by burning the hydrocarbon at a high temperature. The steam in the dehydrogenation reaction also acts as a heat carrier to assist in the gasification of the organic deposits on the catalyst, which interferes with the carbonization of the catalyst and converts the deposited carbides into carbon monoxide and carbon dioxide. It also has the advantage of increasing the active time of the catalyst and moving the reaction equilibrium of dehydrogenation to the product side by steam.

However, since most of the oxidative dehydrogenation reaction is performed at a relatively low reaction temperature of 500 ° C or less, there is a disadvantage that the reaction heat must be externally supplied, and the selectivity of the generated propylene is high but the propane conversion is low, There are low disadvantages.

It is therefore an object of the present invention to provide a hydrogen acceptor for dehydrogenation reaction which can enhance the selectivity and energy efficiency of propylene, butene or butadiene by lowering the reaction temperature by inducing the equilibrium reaction of the dehydrogenation reaction to the reaction, And a process for producing propylene, butene or butadiene from propane or butane.

In order to achieve the above object, the present invention provides a method for producing a catalyst, comprising the steps of: (a) adding 0.1 to 5 parts by weight of platinum, chromium, vanadia and a mixture thereof (content: 100 parts by weight of the carrier) Filling a dehydrogenation catalyst and a copper oxide (content: 0.5 to 40 parts by weight, based on 100 parts by weight of the carrier) carrying a main metal on a carrier, with a hydrogen acceptor supported on the carrier; (b) continuing the oxidative-dehydrogenation reaction while continuously passing propane or butane through the catalyst bed of the reactor; (c) obtaining propylene, butene or butadiene, wherein the hydrogen acceptor is produced by reacting hydrogen produced by a dehydrogenation reaction with lattice oxygen of its own to produce water from propane or butane to produce propylene, butene or butadiene ≪ / RTI >

The process for producing propylene, butene or butadiene from propane or butane using a hydrogen acceptor for dehydrogenation reaction according to the present invention is characterized in that hydrogen generated by the dehydrogenation reaction of propane or butane is reacted with lattice oxygen to remove water in the form of water, And the conversion efficiency is improved by lowering the reaction temperature. Thus, the selectivity of propylene, butene or butadiene is improved and thus the energy efficiency is excellent.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a gas phase reaction apparatus for explaining production of propylene from propane which is an example of the present invention. FIG.
2 is a graph showing the reaction performance of the hydrogen receptor of the present invention.
3 is a graph showing the results of XRD analysis of the catalysts prepared in Examples 2 and 3. FIG.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

The process for producing propylene, butene or butadiene (C3 to C4 alkene) from a hydrogen acceptor for dehydrogenation reaction according to the present invention and propane or butane (C3 to C4 alkane) using the same provides a dehydrogenation catalyst and a hydrogen acceptor A step of filling, propane or butane is continuously passed through the catalyst bed of the reactor, and an oxidative-dehydrogenation reaction is carried out, and propylene, butene or butadiene is obtained.

The hydrogen acceptor (oxygen transfer material) serves to react hydrogen generated by the dehydrogenation reaction with its own lattice oxygen to remove it in the form of water, and copper oxide is supported on the carrier.

Since the copper oxide is reduced by hydrogen, the lattice oxygen reacts with the generated hydrogen to generate water, thereby removing the hydrogen. When the content of the copper oxide is too small, If it is too high, the size of the reactor becomes too large and the cost required for the process increases, which may be uneconomical.

The hydrogen acceptor may further include a manganese oxide. If the content of manganese is too small, the activation of the lattice oxygen may not be smooth. If the content of manganese is too small, the content of copper oxide may be relatively decreased and the effect of increasing the conversion ratio may be deteriorated .

The content of the copper oxide in the hydrogen acceptor is 0.5 to 40 parts by weight, preferably 0.8 to 25 parts by weight, based on 100 parts by weight of the support. When the manganese oxide is included, Is 0.1 to 5 parts by weight, preferably 0.13 to 3 parts by weight, based on 100 parts by weight of the carrier. If the amount of the copper oxide is too small, the effect of increasing the conversion rate may be small, and if it is too large, the cost required for the process may increase, which may be uneconomical. If the content of the manganese oxide is too small, the activation of the lattice oxygen is small and the amount of the metal oxide may be large. If the content of the manganese oxide is too large, the amount of the copper oxide may be relatively decreased.

The hydrogen acceptor is supported at 90 to 300 占 폚, preferably at 90 to 300 占 폚, by supporting a copper compound (e.g., copper nitrate, etc.) and distilled water on a carrier (including manganese compounds such as manganese nitrate, Is dried at a temperature of 100 to 280 DEG C for 8 to 18 hours, preferably 10 to 14 hours, and dried at a temperature of 400 to 1,000 DEG C, preferably 600 to 800 DEG C, for 2 to 8 hours, preferably 3 To < RTI ID = 0.0 > 6 hours. ≪ / RTI & gt ; The content of the copper compound, the distilled water and the manganese compound is 0.5 to 40 parts by weight, preferably 0.8 to 25 parts by weight, and the content of the distilled water is 55 to 100 parts by weight based on 100 parts by weight of the carrier. 99.4 parts by weight, preferably 72 to 99.79 parts by weight, and the content of the manganese compound is 0.1 to 5 parts by weight, preferably 0.13 to 3 parts by weight.

The dehydrogenation catalyst has a form in which a main metal such as platinum, chromium, vanadia (vanadium oxide) and a mixture thereof is supported on a carrier using a solvent, preferably a hydrochloric acid or an ethanol solvent, Of an auxiliary metal.

In the dehydrogenation catalyst, the content of the main metal is 0.1 to 5 parts by weight, preferably 0.3 to 4 parts by weight, and the content of the subsidy is 0.1 to 6 parts by weight, preferably 0.2 To 5 parts by weight. If the content of the main metal is too small, the dehydrogenation reaction may be lowered and the yield may be decreased or the deactivation rate of the catalyst may be increased. If too large, the dehydrogenation reaction may be too strong and the efficiency may be lowered. And may be uneconomical. Also, if the content of the subsidy is too small, the strong hydrogenation function of the main metal may not be controlled, and if it is too large, the function of the main metal may be too weak to increase the yield and decrease catalyst deactivation.

In the hydrogen acceptor and the dehydrogenation catalyst, when the main metals are carried on a carrier, there is no great relation in the introduction order, and the two metals may be sequentially carried or simultaneously carried, It should be present in the state of being. Particularly, it is expected that platinum should be present at a distance close to such an extent that it can be bonded to the auxiliary metal or affect each other electrically or chemically, rather than being independently present in the catalyst.

That is, when the main metal exists singly, side reactions as described above may occur due to the high hydrogenation activity of platinum. However, when the subsidium is bonded to the main metal or exists at a sufficiently close distance, the ensemble effect or the ligand effect The high hydrogenation activity of the main metal is suppressed due to the mutual action of the metal components that can be expected, and the yield and the deactivation rate of the optimum propylene, butene or butadiene can be expected to be reduced.

The carrier can be any commonly used alumina, preferably theta (-a) -alumina, gamma (-gal) -alumina and alpha (alpha) -alumina.

The mixing ratio of the hydrogen acceptor and the dehydrogenation catalyst is 1: 0.1 to 1, preferably 1: 0.2 to 0.8. If the mixing ratio of the hydrogen acceptor and the dehydrogenation catalyst is out of the above range, the equilibrium reaction may not be sufficiently induced by the reaction, or the dehydrogenation reaction may be lowered. In addition, the catalyst layer has a particle size of 280 to 5,000 μm, preferably 350 to 4,000 μm, and if the particle size of the catalyst layer is out of the above range, the efficiency may be low.

The propane and butane may be appropriately selected depending on the amount to be produced. For example, when 0.1 to 1 g of the dehydrogenation catalyst and 0.5 to 1.5 g of the hydrogen acceptor are used, 10 to 50 ml / min, preferably 20 to 40 ml / min.

In the process for producing propylene, butene or butadiene from propane or butane according to the present invention, when butane is used, butene and butadiene are generated in accordance with the dehydrogenation reaction of butane, and accordingly, Butene and butadiene can be separated and used by a method such as a sulfuric acid absorption method, an adsorption separation step, and a distillation extraction method.

1 is a schematic view of a gas phase reaction apparatus for explaining the production of propylene from propane which is an example of the present invention. As shown in FIG. 1, the process for producing propylene from propane according to the present invention comprises first separating the dehydrogenation catalyst and the hydrogen acceptor into a particle size of 280 to 5,000 μm using a testing sieve, Prepare the mixture. Wherein the mixing ratio of the hydrogen acceptor to the dehydrogenation catalyst is 1: 0.1 to 1. Next, a quartz reactor 12 is filled with the catalyst mixture, the quartz reactor 12 is mounted to a furnace 14, and a mass flow controller (Mass Flow Controller) The temperature of the electric furnace 14 is raised to 500 to 700 占 폚, preferably 600 占 폚, using a temperature controller 26 while supplying nitrogen and / The supply of nitrogen and / or air is stopped, propane 18 is supplied at a rate of 10 to 50 ml / min and, if necessary, hydrogen (20) at a rate of 5 to 40 ml / min. To 6 hours to produce propylene. When the lattice oxygen of the hydrogen acceptor reacts with hydrogen due to the dephosphorylation reaction, the supply of propane (18) is stopped and air, preferably oxygen, Oxygen is replenished, and then the above process is repeated Propylene can be produced. When the catalyst mixture is filled in the quartz reactor 12, glass wool may be added as needed to support the dehydrogenation catalyst and the filling layer of the hydrogen acceptor.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

[Example 1] Production of platinum-tin /? -Alumina

The commercially available alumina sphere was used for the θ alumina. 4.5 wt% of tin (Tin II chloride, Sigma-Aldrich, > 98%) was supported on alumina and hydrochloric acid, dried at a temperature of 120 캜 for 12 hours and then calcined at a temperature of 600 캜 for 3 hours, / θ alumina. Next, 3 wt% of platinum (hydrogen hexachloroplatinate IV hydrate, KOJIMA CHEMICALS) was supported on tin /? Alumina in the same manner as above to prepare platinum-tin /? -Alumina.

[Example 2] Preparation of copper-manganese / y-alumina

A solution of 1.05% by weight of copper nitrate trihydrate (JUNSEI), 0.16% by weight of manganese Ⅱ nitrate hexahydrate (JUNSEI) and 98.79% by weight of distilled water was supported on 10 g of γ-alumina using a rotary concentrator, (CuO concentration: 8% by weight, MnO 2 concentration: 0.4% by weight) was prepared by drying the mixture at a temperature of 50 ° C for 12 hours and then calcining at a temperature of 750 ° C for 5 hours.

[Example 3] Production of copper /? Alumina

1.05% by weight of copper nitrate trihydrate (JUNSEI) and 98.95% by weight of distilled water were carried on 10 g of alpha alumina using a rotary concentrator, dried at 120 DEG C for 12 hours, Lt; 0 > C for a period of time to prepare copper / alpha -alumina (CuO concentration: 11% by weight).

[Example 5] Production of propylene from propane

The dehydrogenation catalyst prepared in Example 1 (platinum-tin /? -Alumina,

Figure pat00001
0.5 g of Pt-Sn / Al 2 O 3 and 0.5 cc of the hydrogen acceptor (copper-manganese / y-alumina) prepared in Example 2 were mixed and then the glass wool Was put into a quartz reactor and filled with a mixture of the dehydrogenation catalyst and the hydrogen acceptor. The quartz reactor was placed in an electric furnace, and the temperature of the electric furnace was raised to 576.5 캜 while nitrogen was supplied at a rate of 32 ml / min for 1 hour, maintained at a temperature of 576.5 캜 for 5 minutes, The supply was stopped, and propylene was reacted for 4 minutes while supplying propane as a reaction gas at a rate of 32 ml / min and hydrogen at a rate of 32 ml / min.

[Example 6] Production of propylene from propane

Propylene was prepared in the same manner as in Example 5 except that the hydrogen acceptor (copper /? Alumina) prepared in Example 3 was used in place of the hydrogen acceptor prepared in Example 2.

[Comparative Example 1] Production of propylene from propane

Propylene was prepared in the same manner as in Example 4 except that a glass bead was used in place of the hydrogen acceptor.

[Experimental Example 1] Evaluation of hydrogen receptor performance

In the process of preparing propylene by the methods of Examples 5 and 6 and Comparative Example 1, the gas was sampled and analyzed to confirm the activity of the catalyst layer. The column was connected to a capillary column (GS-Alumina, Agilent Technologies, USA, Id: 0.53 mm, Length: 50 m) was used. The propane conversion was determined by the following equation (1), propylene selectivity by the following equation (2), and propylene yield by the following equation (3) Respectively.

[Equation 1]

Figure pat00002

&Quot; (2) "

Figure pat00003

&Quot; (3) "

Figure pat00004

In Formula 1 and 2, n (C 3 H 8 ) represents the in, out the number of moles of propane, n (CH 4), n (C 2 H 6), n (C 2 H 4) , and n (C 3 H 6 ) represent the number of moles of methane, ethane, ethene and propene out, respectively.

2 is a graph showing the reaction performance of the hydrogen receptor of the present invention. As shown in FIG. 2, the conversion, selectivity, and yield of propylene were shown in a propane dehydrogenation reaction experiment of a platinum catalyst mixed with an oxide not subjected to reduction. As a result, it was found that the catalysts not subjected to reduction were most excellent in conversion, selectivity, and yield, and the conversion, selectivity, and yield of the hydrogen acceptor of the present invention were excellent.

[Experimental Example 2] Nitrogen adsorption / desorption analysis of hydrogen acceptor

The specific surface area, pore volume, and pore size were measured by a nitrogen adsorption / desorption analysis (Brunauer-Emmett-Teller equation, BET analysis) of a mixture of the hydrogen acceptor prepared in Examples 2 and 3, Respectively.

Specific surface area (m 2 g -1 ) Pore volume (cm 3 g -1 ) Pore size (nm) Copper manganese (y-alumina) 148.98 0.4578 12.29 Copper (alpha alumina) 3.59 0.0104 11.62

3 is a graph showing the results of XRD analysis of the catalysts prepared in Examples 2 and 3. FIG. As can be seen from Table 1 and FIG. 2, the specific surface area and the pore volume showed a higher value than that of the copper-manganese / y-alumina (b in FIG. 2) The copper / alpha alumina oxide (a in Fig. 2) showed the smallest value. The pore volume of copper - manganese / γ - alumina was the largest.

Claims (7)

(a) a dehydrogenation catalyst in which a main metal selected from the group consisting of platinum, chromium, vanadia, and a mixture thereof (content: 0.1 to 5 parts by weight with respect to 100 parts by weight of the support) Filling copper oxide (content: 0.5 to 40 parts by weight with respect to 100 parts by weight of the carrier) of the hydrogen acceptor supported on the carrier;
(b) continuing the oxidative-dehydrogenation reaction while continuously passing propane or butane through the catalyst bed of the reactor;
(c) obtaining propylene, butene or butadiene,
Wherein the hydrogen acceptor reacts hydrogen generated by the dehydrogenation reaction with its lattice oxygen to produce water. ≪ Desc / Clms Page number 20 > 3. The process according to claim 1, wherein the hydrogen acceptor further comprises manganese oxide (content: 0.1 to 5 parts by weight based on 100 parts by weight of the carrier) supported on the carrier, wherein propylene or butene is produced from propane or butane. Way. The process for producing propylene, butene or butadiene from propane or butane according to claim 1, wherein the reaction of step (b) is carried out at a temperature of 500 to 700 ° C. The hydrogen receptor according to claim 1, wherein the hydrogen acceptor is formed by supporting a copper compound and distilled water on a carrier, drying the mixture at a temperature of 90 to 300 ° C. for 8 to 18 hours, and calcining the mixture at a temperature of 400 to 1,000 ° C. for 2 to 8 hours And,
Wherein the content of the copper compound is from 0.5 to 40 parts by weight based on 100 parts by weight of the carrier, and the content of distilled water is from 55 to 99.4 parts by weight based on 100 parts by weight of the carrier. The process for producing propylene, butene or butadiene from propane or butane according to claim 1, wherein the dehydrogenation catalyst and the hydrogen acceptor have a particle size of 280 to 5,000 m. The process for producing propylene, butene or butadiene from propane or butane according to claim 1, wherein the carrier is alumina. The process for producing propylene, butene or butadiene from propane or butane according to claim 1, wherein the dehydrogenation catalyst further comprises tin (content: 0.1 to 6 parts by weight based on 100 parts by weight of the support) as an auxiliary metal.
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WO2020138600A1 (en) * 2018-12-28 2020-07-02 에스케이가스 주식회사 Catalyst for preparing olefins, including oxygen carrier material and dehydrogenation catalyst
CN113226540A (en) * 2018-12-28 2021-08-06 Sk燃气 株式会社 Catalyst for the production of olefins comprising an oxygen carrier material and a dehydrogenation catalyst
US11865514B2 (en) 2018-12-28 2024-01-09 Sk Gas Co., Ltd. Catalyst for producing olefin, including oxygen carrier material and dehydrogenation catalyst
CN113226540B (en) * 2018-12-28 2024-03-26 Sk燃气 株式会社 Catalyst for olefin production comprising oxygen carrier material and dehydrogenation catalyst

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