KR20170007636A - Catalysts for preparing Olefin by Dehydrogenation of Hydrocarbon, and Preparation Method Thereof - Google Patents
Catalysts for preparing Olefin by Dehydrogenation of Hydrocarbon, and Preparation Method Thereof Download PDFInfo
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- KR20170007636A KR20170007636A KR1020150098248A KR20150098248A KR20170007636A KR 20170007636 A KR20170007636 A KR 20170007636A KR 1020150098248 A KR1020150098248 A KR 1020150098248A KR 20150098248 A KR20150098248 A KR 20150098248A KR 20170007636 A KR20170007636 A KR 20170007636A
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
- C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
- C07C5/41—Catalytic processes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
- B01J2523/13—Potassium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
- B01J2523/37—Lanthanides
- B01J2523/3712—Cerium
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- 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
- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to a catalyst for hydrocarbon dehydrogenation reaction, a process for preparing the same, and a process for preparing olefins by dehydrogenating hydrocarbon using the catalyst, and more particularly, to an alumina support on which chromium oxide, potassium oxide and cerium oxide are supported 1 to 30 parts by weight of chromium oxide with respect to 100 parts by weight of alumina, 0.1 to 10 parts by weight of potassium oxide with respect to 100 parts by weight of alumina and 1 to 20 parts by weight of cerium oxide with respect to 100 parts by weight of alumina, Thereby providing a reaction catalyst. In the catalyst for hydrocarbon dehydrogenation reaction of the present invention, the alumina support can be easily prepared by the spray drying method, and the process of supporting the metal oxide is also carried out through a simple process. Therefore, excellent reproducibility can be secured in the production process of a catalyst for hydrocarbon dehydrogenation reaction containing alumina carrier and ultimately obtained alumina-supported chromium oxide-potassium oxide-cerium oxide. Therefore, a catalyst for hydrocarbon dehydrogenation reaction which can produce olefins with high yield can be stably obtained. In addition, for example, it is possible to obtain an economical benefit by satisfying propylene demand by securing a proprietary production process capable of continuously producing propylene without newly introducing a naphtha cracking process, and being able to actively cope with future market changes .
Description
The present invention relates to a catalyst for the production of olefins through dehydrogenation of hydrocarbons and a process for their preparation.
Olefins such as ethylene and propylene are widely used in the petrochemical industry. Generally these olefins are obtained in the pyrolysis process of naphtha. However, since higher amounts of olefins are required in the petrochemical industry, olefins are also produced by dehydrogenation processes using catalysts of lower hydrocarbons.
For example, propylene, together with ethylene, is the most basic material used as a metric for the petrochemical industry, which can be structurally converted to a variety of chemicals with both methyl and allylic groups at the same time. Typically, it is mainly used for the production of polypropylene which is a thermoplastic plastic. In addition, it is used as a raw material for acrylonitrile, propylene oxide, epoxy resin, oxoalcohol, isopropyl alcohol and the like.
Until now, most of the propylene has been produced with ethylene by steam cracking naphtha, which is produced as a byproduct in crude cracking process or distillation of crude oil. However, the present ethylene production technology is concentrated in an economical gas decomposition process, making it difficult to expand the existing naphtha cracking process, thus limiting the supply of propylene. In addition, the global demand for propylene used in automobiles and electronic materials, especially in China and India, has surged, and the imbalance of demand and demand for propylene will increase further.
Therefore, propylene feed-on-purge technology for solving the above problem has become a big issue. Particularly, C4-C8 olefin conversion process (non-patent document 1), olefin metathesis process (non-patent document 2) -propylene process (non-patent document 3), and a process for dehydrogenating propane (non-patent document 4). Among the above processes, propane dehydrogenation process has attracted the most attention as the demand for propylene for propane and the demand for eco-friendly energy production have increased, and development of shale gas and tight oil has been activated mainly in North America As the price of propane declines, the economy is expected to increase further.
The present propane dehydrogenation process technologies are based on noble metal catalysts or noncontinuous processes, and even in the case of continuous processes, there is a problem in operation of the catalyst layer, and it is known that it is not suitable for the production of large quantities of propylene with a scale of several million tons (see Patent Documents 1 to 3) 3). In addition, propane dehydrogenation reaction thermodynamically limits the conversion of propane to hydrogen due to the reversible reaction. In order to overcome this problem, most processes use external oxidizing agents such as oxygen, halogen, sulfur compounds, carbon dioxide, Hydrogen is converted into water (Non-Patent Document 5). Therefore, in order to effectively mass-produce propylene, it is required to develop a new propane dehydrogenation process which solves the above-mentioned problems of the continuous process and reduces the production cost by using a low cost noble metal catalyst without an oxidizer.
Among the catalysts used for propane dehydrogenation, noble metal catalysts are catalyzed by a direct dehydrogenation mechanism in which hydrogen is adsorbed to active sites (Non-Patent Document 6). In the case of transition metal oxides, the mechanism of partial oxidation of lattice oxygen van Krevelen mechanism). Therefore, when the metal oxide catalyst is used, the dehydrogenation reaction can be performed only with the lattice oxygen, and therefore, a high propylene yield can be expected without oxidizing agent if the amount of lattice oxygen and the delivery rate are maximized. As the transition metal catalyst currently in use, there is a catalyst in which chromium oxide (Patent Document 4) or vanadium oxide (Patent Document 5) is supported on an alumina support in an active phase, A small amount of an alkali metal component may be simultaneously carried in order to suppress the formation. However, because of the limitation of the lattice oxygen content, propylene can not be obtained in a sufficient yield without using an oxidizing agent, so that more efficient catalyst research is needed.
Therefore, the inventors of the present invention have conducted continuous research to improve the low activity of the chromium oxide catalyst, which has been shown in the prior art, by using a transition metal oxide catalyst having cerium oxide, potassium oxide, and cerium oxide A process for the preparation of olefins was developed using a catalyst prepared as described above.
It is an object of the present invention to provide a catalyst for producing olefins through dehydrogenation of hydrocarbons and a process for their preparation.
In order to achieve the above object,
An alumina support on which chromium oxide, potassium oxide and cerium oxide are supported,
1 to 30 parts by weight of chromium oxide relative to 100 parts by weight of alumina,
0.1 to 10 parts by weight of potassium oxide and < RTI ID = 0.0 >
And 1 to 20 parts by weight of cerium oxide relative to 100 parts by weight of alumina.
In addition,
Spray drying a raw material solution containing an aluminum precursor to prepare an alumina support (step 1);
Impregnating the alumina support of step 1 with a mixed solution comprising a chromium precursor, a potassium precursor and a cerium precursor (step 2);
And drying and heat-treating the resultant obtained in the step 2 (step 3). The present invention also provides a method for producing a catalyst for a hydrocarbon dehydrogenation reaction.
Further,
Preparing olefins from hydrocarbons using the catalyst (step 1);
Separating the catalyst used in the step 1 and the produced olefin and regenerating the separated catalyst (step 2); And
(Step 3) recycling the catalyst recovered in
The above steps 1 to 3 are repeatedly carried out to continuously recover the catalyst and prepare the olefin.
Further,
(Step 1) of pre-treating the catalyst by supplying a reducing gas to the catalyst for producing olefins from hydrocarbons;
Preparing olefins from hydrocarbons using the catalyst pretreated in step 1 (step 2);
Separating the catalyst used in the
(Step 4) of recycling the catalyst recovered in step 3 to the process of step 1,
The above steps 1 to 4 are repeatedly carried out to continuously regenerate the catalyst and produce the olefin.
In the catalyst for hydrocarbon dehydrogenation reaction of the present invention, the alumina support can be easily prepared by the spray drying method, and the process of supporting the metal oxide is also carried out through a simple process. Therefore, excellent reproducibility can be secured in the production process of a catalyst for hydrocarbon dehydrogenation reaction containing alumina carrier and ultimately obtained alumina-supported chromium oxide-potassium oxide-cerium oxide. Therefore, a catalyst for hydrocarbon dehydrogenation reaction which can produce olefins with high yield can be stably obtained.
According to the present invention, it is possible to easily produce propylene, which is a kind of olefin, from hydrocarbons, whose demand and value are gradually increasing globally. In addition, for example, it is possible to obtain an economical benefit by satisfying propylene demand by securing a proprietary production process capable of continuously producing propylene without newly introducing a naphtha cracking process, and being able to actively cope with future market changes .
1 is a graph showing a nitrogen adsorption / desorption isotherm of a catalyst for hydrocarbon dehydrogenation reaction (17.5Cr-2K-XCe / Al) of Example 1;
2 is a graph showing the X-ray diffraction analysis results of the catalyst for hydrocarbon dehydrogenation reaction (17.5Cr-2K-XCe / Al) of Example 1;
3 is a graph showing the results of hydrogen-heating reduction of the catalyst for hydrocarbon dehydrogenation reaction (17.5Cr-2K-XCe / Al) of Example 1;
4 is a graph showing catalytic activity for dehydrogenation of propane under the catalyst for hydrocarbon dehydrogenation reaction (17.5Cr-2K-XCe / Al) of Example 2. Fig.
According to the present invention,
An alumina support on which chromium oxide, potassium oxide and cerium oxide are supported,
1 to 30 parts by weight of chromium oxide relative to 100 parts by weight of alumina,
0.1 to 10 parts by weight of potassium oxide and < RTI ID = 0.0 >
And 1 to 20 parts by weight of cerium oxide relative to 100 parts by weight of alumina.
The catalyst for the hydrocarbon dehydrogenation reaction of the present invention is a catalyst comprising an alumina support on which chromium oxide, potassium oxide and cerium oxide are supported for producing an olefin of higher yield. The catalyst can have high activity by simultaneously supporting cerium oxide, potassium oxide, and cerium oxide, which is excellent in the ability to provide oxygen, to the alumina carrier, while conventional chromium oxide catalysts have low activity. In addition, the conventional noble metal catalyst is reacted by a direct dehydrogenation mechanism in which hydrogen is adsorbed to the active site, while the metal oxide catalyst can be dehydrogenated only by lattice oxygen. Therefore, if the amount of the lattice oxygen in the catalyst and the delivery rate are maximized, the catalyst reacts with hydrocarbons at a high frequency without an oxidizing agent to produce an olefin of excellent yield.
Wherein the catalyst comprises an alumina support carrying chromium oxide, potassium oxide and cerium oxide, and comprises 1 to 30 parts by weight of chromium oxide relative to 100 parts by weight of alumina, 0.1 to 10 parts by weight of potassium oxide and 100 parts by weight of
In the catalyst, the weight ratio of chromium oxide to 100 parts by weight of alumina may be 1 to 30 parts by weight, and preferably 15 to 25 parts by weight. The weight ratio of potassium oxide to alumina may be 0.1 to 10 parts by weight, preferably 0.5 to 3.5 parts by weight based on 100 parts by weight of alumina. Further, the weight ratio of cerium oxide to alumina may be 1 to 20 parts by weight, preferably 1 to 4 parts by weight based on 100 parts by weight of alumina.
In particular, the chromium oxide, potassium oxide and cerium oxide may have 17.5 parts by weight, 2 parts by weight and 1 to 2 parts by weight, respectively, based on 100 parts by weight of alumina.
The catalyst may be used as a process for producing propylene through a dehydrogenation process of propane, but is not limited thereto.
In addition,
Spray drying a raw material solution containing an aluminum precursor to prepare an alumina support (step 1);
Impregnating the alumina support of step 1 with a mixed solution comprising a chromium precursor, a potassium precursor and a cerium precursor (step 2);
(3) drying and heat-treating the resultant obtained in the step (2). The catalyst for a hydrocarbon dehydrogenation reaction according to claim 1,
Hereinafter, the method for producing the catalyst for hydrocarbon dehydrogenation reaction according to the present invention will be described in detail.
In the method for producing a catalyst for hydrocarbon dehydrogenation reaction according to the present invention, step 1 is a step of spray drying a raw material solution containing an aluminum precursor to prepare an alumina support.
The aluminum precursor of step 1 above can be applied to any of the commonly used precursors. In general, as a precursor of aluminum, it is preferable to use at least one selected from a hydroxide precursor of aluminum, a nitrate precursor or a chloride precursor, and more preferably, an aluminum hydroxide precursor is used.
In addition, the above step 1 more specifically includes a step of dissolving an aluminum precursor in a first solvent to prepare a precursor solution of aluminum, a step of preparing a carrier forming solution by mixing an acid aqueous solution with the prepared precursor solution, Stirring the solution for forming a carrier, spray drying it to obtain a solid material, and then heat-treating it to obtain an alumina support for a hydrocarbon dehydrogenation reaction catalyst.
The first solvent is preferably at least one selected from water and alcohol, and more preferably water. Here, with respect to the mixing ratio of the aluminum precursor and the first solvent to be used, the weight ratio of the aluminum precursor and the first solvent is preferably 1: 0.5 to 3.5, more preferably 1: 2.
The acid aqueous solution is preferably at least one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and the like, more preferably nitric acid. The concentration of the acid aqueous solution used in the above is preferably 0.1 to 20 parts by weight, more preferably 5 parts by weight, relative to the precursor solution.
The spray drying can be carried out in a temperature range of 50 to 300 DEG C with an atomizer at a rotation range of 2000 to 10000 rpm for 1 to 60 hours, preferably at a temperature range of 100 to 250 DEG C, And then heat-dried at a rotation range of 4000 to 8000 rpm for 30 to 50 hours to obtain an alumina support.
The heat treatment may be performed in a temperature range of 400 to 1200 ° C for 1 to 12 hours, preferably in a temperature range of 500 to 800 ° C for 4 to 8 hours to obtain an alumina support.
In the method for producing a catalyst for hydrocarbon dehydrogenation reaction according to the present invention,
The chromium precursor of
The amount of the chromium precursor used in
The potassium precursor of
The amount of the potassium precursor used in
In
The amount of the cerium precursor used in
In the method for producing a catalyst for hydrocarbon dehydrogenation reaction according to the present invention, Step 3 is a step of drying and heat-treating the resultant obtained in
The drying is performed to remove moisture remaining after impregnating the metal precursor salt. Drying temperature and drying time can be limited according to general drying conditions. For example, the drying can be carried out at a temperature of 50 to 200 DEG C, preferably 70 to 120 DEG C for 3 to 48 hours, preferably 6 to 18 hours.
In addition, the heat treatment is for dissolving the metal precursor salts and synthesizing the metal precursor salt supported on the alumina support as the chromium oxide-potassium oxide-cerium oxide. The heat treatment can be performed at a temperature range of 350 to 1000 ° C, preferably 500 to 700 ° C, for 1 to 8 hours, preferably 3 to 6 hours.
Further,
Preparing olefins from hydrocarbons using the catalyst (step 1);
Separating the catalyst used in the step 1 and the produced olefin and regenerating the separated catalyst (step 2); And
(Step 3) recycling the catalyst recovered in
The above steps 1 to 3 are repeatedly carried out to continuously recover the catalyst and prepare the olefin.
Hereinafter, the continuous reaction-regeneration and flow-type olefin production process using the catalyst for hydrocarbon dehydrogenation reaction according to the present invention will be described in detail.
In the continuous reaction-regeneration and flow-type olefin production process using the catalyst for hydrocarbon dehydrogenation reaction according to the present invention, step 1 is a step of producing olefins from hydrocarbons using a catalyst for hydrocarbon dehydrogenation reaction.
Wherein the catalyst of step 1 comprises an alumina carrier on which chromium oxide, potassium oxide and cerium oxide are supported, and 1 to 30 parts by weight of chromium oxide with respect to 100 parts by weight of alumina, 0.1 to 10 parts by weight of potassium oxide And 1 to 20 parts by weight of cerium oxide relative to 100 parts by weight of alumina.
Unlike conventional chromium oxide catalysts having low activity, the catalysts can have high activity by simultaneously supporting chromium oxide, potassium oxide, and cerium oxide, which are excellent in oxygen supplying ability, on the alumina carrier. Also, in the conventional noble metal catalyst, the reaction proceeds by a direct dehydrogenation mechanism in which hydrogen is adsorbed to the active site, while the catalyst can be dehydrogenated only by lattice oxygen. Therefore, if the amount of the lattice oxygen in the catalyst and the delivery rate are maximized, the catalyst reacts with hydrocarbons at a high frequency without an oxidizing agent to produce an olefin of excellent yield. On the other hand, the support may be, for example, alumina, but is not limited thereto, and the catalyst may be applied by selecting an appropriate material that can be used as a carrier of the catalyst.
In the preparation of olefins in the step 1, the contact time of the catalyst for hydrocarbon dehydrogenation reaction with hydrocarbon as a starting material may be 0.5 to 10 seconds, preferably 2 to 3 seconds.
If the contact time of the hydrocarbon and the catalyst is less than 0.5 second, the conversion rate of the hydrocarbon decreases. If the contact time exceeds 10 seconds, the amount of the active lattice oxygen involved in the lattice oxygen of the catalyst sharply decreases The selectivity of the olefin may decrease.
Further, for example, the above production method can be applied as a method for producing propylene by the dehydrogenation reaction of propane. The reaction temperature for progressing the reaction is preferably 300 to 800 ° C, more preferably 500 to 700 ° C. If the reaction temperature is lower than 400 ° C, propane may not be sufficiently activated. If the reaction temperature is higher than 800 ° C, decomposition of propane may occur.
When the reactant is fed to the reactor in the dehydrogenation reaction of propane, the amount of the reactant to be injected can be controlled using a mass flow rate controller. The amount of the reactant to be injected is preferably 100 to 20000 (GHSV) h - 1 , but is not limited thereto.
In the production method according to the present invention,
The catalyst reacted in step 1 above can be regenerated by reaction with oxygen after being separated from the olefin.
In the production method according to the present invention, step 3 is a step of recirculating the catalyst regenerated in
By feeding the catalyst regenerated in
In addition, since the reaction for regenerating the catalyst in the
The production method of the present invention is advantageous in that olefin can be continuously produced as well as the economical efficiency of the process can be further improved because the catalyst used for olefin production can be regenerated and used repeatedly.
Further,
(Step 1) of pre-treating the catalyst by supplying a reducing gas to the catalyst for producing olefins from hydrocarbons;
Preparing olefins from hydrocarbons using the catalyst pretreated in step 1 (step 2);
Separating the catalyst used in the
(Step 4) of recycling the catalyst recovered in step 3 to the process of step 1,
The above steps 1 to 4 are repeatedly carried out to continuously regenerate the catalyst and produce the olefin.
Hereinafter, the continuous reaction-regeneration method and the liquid olefin production method using the catalyst for hydrocarbon dehydrogenation reaction after the reducing gas pretreatment according to the present invention will be described in detail for each step.
In the continuous reaction-regeneration and flow-type olefin production method using the catalyst for hydrocarbon dehydrogenation reaction after the reducing gas pretreatment according to the present invention, step 1 is a step of supplying a reducing gas to the catalyst for hydrocarbon dehydrogenation reaction for producing olefins from hydrocarbons Thereby pretreating the catalyst.
The process of the present invention is particularly directed to a dehydrogenation process for producing olefins from hydrocarbons. When olefins are prepared from hydrocarbons through a catalyst in the prior art, the temperature of the catalyst rapidly increases at the beginning of the reaction as the reaction time elapses, and then the temperature gradually increases As shown in Fig.
At this time, in the early stage of the reaction in which the temperature of the catalyst is increased, non-olefinic by-products are generated from hydrocarbons, and olefins are produced from hydrocarbons starting from the point when the temperature of the catalyst gradually decreases. Therefore, it can be seen that during the production of olefins from hydrocarbons, for the first half of the reaction, for example, for about 5 seconds from the start of the reaction, is an unnecessary part for the production of olefins.
Thus, in the production method of the present invention, in order to prevent the efficiency of the catalyst from being lowered due to the reaction period in which carbon dioxide, which is a by-product, is generated, the reducing gas is supplied to the catalyst for producing olefins from hydrocarbons The catalyst is pretreated.
In the pretreatment of step 1, the catalyst before the hydrocarbons are pre-treated in advance to increase the temperature, so that olefins can be produced instantaneously without a zone where byproducts are generated when the catalyst is supplied with hydrocarbon.
At this time, the pretreatment of step 1 may be performed by contacting the catalyst with a reducing gas for 0.5 to 5 seconds. If the contact between the catalyst and the reducing gas is less than 0.5 second, the catalyst may not be optimized according to the pretreatment in Step 1, and when the contact between the catalyst and the reducing gas exceeds 5 seconds, the yield of the olefin The problem may be degraded.
At this time, the reducing gas in step 1 may include at least one hydrocarbon having a linear or branched C 1 to C 4 alkene structure.
Alternatively, the reducing gas of step 1 may include at least one hydrocarbon having a linear or branched C 1 to C 4 alkene structure,
Or hydrocarbons having a C 1 to C 4 alkane structure.
Meanwhile, the reducing gas in step 1 may include a gas such as carbon monoxide, hydrogen, ethylene, ethane, and methane. The gas such as carbon monoxide can react with oxygen on the surface of the highly reactive catalyst to pre-treat the catalyst, and the temperature of the catalyst rises due to the heat generated by the pretreatment.
In addition, the reducing gas of step 1 may be a by-product produced from the hydrocarbon at the production of the olefin. When olefins are produced from hydrocarbons, carbon monoxide, hydrogen, ethylene, ethane, and methane are usually generated as by-products. The production method of the present invention can be used as a reducing gas for pretreating a catalyst such as carbon monoxide generated as a by-product, thereby reducing the manufacturing cost.
In the production process of the present invention,
In the present invention, since the catalyst of
Wherein the catalyst comprises an alumina support carrying chromium oxide, potassium oxide and cerium oxide, and comprises 1 to 30 parts by weight of chromium oxide relative to 100 parts by weight of alumina, 0.1 to 10 parts by weight of potassium oxide and 100 parts by weight of
In the preparation of the olefin in the
If the contact time of the hydrocarbon and the catalyst is less than 0.5 second, the conversion rate of the hydrocarbon decreases. If the contact time exceeds 10 seconds, the amount of the active lattice oxygen involved in the lattice oxygen of the catalyst sharply decreases The selectivity of the olefin may decrease.
Further, for example, the above production method can be applied as a method for producing propylene by the dehydrogenation reaction of propane. The reaction temperature for progressing the reaction is preferably 300 to 800 ° C, more preferably 500 to 700 ° C. If the reaction temperature is lower than 400 ° C, propane may not be sufficiently activated. If the reaction temperature is higher than 800 ° C, decomposition reaction of propane may occur.
When the reactant is fed to the reactor in the dehydrogenation reaction of propane, the amount of the reactant to be injected can be controlled using a mass flow rate controller. The amount of the reactant to be injected is preferably 100 to 20000 (GHSV) h - 1 , but is not limited thereto.
In the production process according to the present invention, step 3 is a step of separating the reacted catalyst and olefin produced in
The catalyst reacted in
In the production method according to the present invention, step 4 is a step of recirculating the catalyst regenerated in step 3 to the step 1.
By feeding the catalyst regenerated in step 3 of the present invention to the process of step 1 again, the catalyst can be recycled and olefin can be produced more economically.
In addition, since the reaction for regenerating the catalyst in the step 3 is an exothermic reaction, the temperature of the catalyst can be increased through the generated heat energy, so that the pretreatment through the reducing gas can be performed more smoothly in the recirculating step 1.
That is, since the energy is supplied to the catalyst by the regeneration of the step 3 in raising the temperature of the catalyst to the temperature required for producing olefins from hydrocarbons, the temperature of the catalyst can be increased more economically.
As described above, the production method of the present invention can improve the production yield of olefin through the pretreatment of the catalyst as well as recycle the catalyst used for olefin production, thereby improving the economical efficiency of the process In addition, there is an advantage that olefins can be continuously produced.
Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
<Production Example>
Step 1: 27.8 g of aluminum hydroxide was dissolved in distilled water (56.8 kg) to prepare an aluminum precursor solution. At the same time, 1.2 kg of nitric acid aqueous solution of 60 parts by weight was mixed with distilled water (14.2 kg) to prepare an aqueous nitric acid solution.
Step 2: The precursor solution prepared in Step 1 was stirred for 30 minutes, then mixed with the nitric acid aqueous solution, and stirred for 40 hours.
Step 3: The mixture of
Step 4: The dried support precursor in step 3 was heat-treated for 6 hours at 650 ° C in an electric furnace in an air atmosphere, and an alumina support was prepared by spray drying.
Example 1 A process for producing a catalyst for hydrocarbon dehydrogenation reaction (17.5Cr-2K-XCe / Al (X = 0, 1, 2, 4, 8 parts by weight)
Step 1: The chromium trioxide precursor and the potassium nitrate precursor were dissolved in distilled water so that the amount of chromium oxide to be supported on the alumina support produced in the above Preparation Example was 17.5 parts by weight based on 100 parts by weight of alumina and the amount of supported potassium oxide was 2 parts by weight Precursor mixture was prepared.
Step 2: A cerium nitrate precursor is injected into the precursor mixture solution of Step 1 so that the amount of cerium oxide supported on the alumina support produced in the preparation example is 0, 1, 2, 4, 8 parts by weight based on 100 parts by weight of alumina Respectively.
Step 3: When the precursor was completely dissolved in the mixed solution prepared in the
Step 4: The solid material prepared in step 3 was dried in an oven at 80 캜 for 12 hours, and then heat-treated at 700 캜 for 4 hours in an air atmosphere.
≪ Example 2 > Preparation of propylene 1
Step 1: To activate the catalyst for hydrocarbon dehydrogenation reaction (17.5Cr-2K-XCe / Al (X = 0, 1, 2, 4, 8 parts by weight) prepared in Example 1), 0.2 g of the catalyst Quartz reactor, and maintained in an oxygen atmosphere at 700 占 폚 for 30 minutes.
Step 2: The catalyst of step 1 was fed to the reaction part lowered to 630 캜, and propane gas composed of 50% by volume of propane and 50% by volume of nitrogen was fed to the reaction part to prepare propylene. At this time, the total flow rate of propane gas with respect to the catalyst mass was maintained at 12,000 ml C3 / h - 1 g cat - 1 .
Step 3: The catalyst reacted with the propylene produced in
Step 4: The catalyst regenerated in the air reaction part was repeatedly carried out in the step 1, and then supplied to the reaction part.
Example 3
Step 1: The catalyst for hydrocarbon dehydrogenation reaction (17.5Cr-2K-XCe / Al (X = 0, 1, 2, 4, 8 parts by weight) prepared in Example 1) Prior to this, hydrogen (H 2 ) was supplied to the catalyst pretreatment section through a reducing gas supply section.
Step 2: The catalyst reacted with hydrogen in the step 1 was fed to the reaction part, and propane gas composed of 50 vol% of propane and 50 vol% of nitrogen was fed to the reaction part to prepare propylene. At this time, the total flow rate of propane gas with respect to the catalyst mass was maintained at 12,000 ml C3 / h - 1 g cat - 1 .
Step 3: The catalyst reacted with the propylene produced in
Step 4: The catalyst regenerated in the air reaction part was repeatedly carried out in the step 1, and then supplied to the reaction part.
<Experimental Example 1> Characterization and comparison of catalysts for hydrocarbon dehydrogenation reaction
The characteristics according to the content of cerium oxide in Example 1 of the present invention were analyzed and the results are shown in Figs. 1 to 3 and Tables 1 and 2, respectively.
(1) Analysis of nitrogen adsorption / desorption isotherms according to cerium oxide content of 17.5Cr-2K-XCe / Al (X = 0, 1, 2, 4, 8 parts by weight) catalyst of Example 1 of the present invention (BEL Japan, BELSORP-mini II), and is shown in Fig. 1 below.
As shown in FIG. 1, 17.5 Cr-2 K-XCe / Al catalysts containing 0, 1, 2, 4, and 8 parts by weight of cerium oxide with respect to 100 parts by weight of alumina all exhibit an IV- Showing the characteristics of typical mesoporous materials. Also, by indicating the Hysteresis Loop of the H2-type, it can be seen that the above-mentioned catalysts mainly formed an ink-bottle type pore structure.
(2) Nitrogen adsorption / desorption experiments according to cerium oxide content of 17.5Cr-2K-XCe / Al (X = 0, 1, 2, 4, 8 parts by weight) catalyst of Example 1 of the present invention (BEL Japan, BELSORP- mini II) results were analyzed by the Brunauer-Emmett-Teller calculation method and are shown in Table 1 below.
(m
2
/ g)
(
cm
3
/ g)
(nm)
As shown in Table 1, the specific surface area of the 17.5Cr-2K-XCe / Al catalyst containing 0, 1, 2, 4, 8 parts by weight of cerium oxide relative to 100 parts by weight of alumina was 120 to 144 m 2 g -1 And the average pore size is about 9.0 to 9.5 nm. It can be seen that the surface area and the pore volume gradually decrease as the cerium loading is increased.
(3) X-ray diffraction analysis (Rigaku, D-5) of 17.5Cr-2K-XCe / Al (X = 0, 1, 2, 4, 8 parts by weight) catalyst of Example 1 of the present invention, Max2500-PC diffractometer) The result graph is shown in FIG.
As shown in FIG. 2, 17.5 Cr-2 K-XCe / Al catalysts containing 0, 1, 2, 4, and 8 parts by weight of cerium oxide exhibited characteristic peaks on gamma alumina with respect to 100 parts by weight of alumina, Characteristic peaks for chromium did not appear. In the case of the catalyst of 17.5Cr-2K-XCe / Al (X = 4, 8 parts by weight), the characteristic peak for cerium oxide was shown, which confirmed that the cerium oxide formed a bulk phase when the amount of cerium oxide increased have.
(4) 0.05 g of 17.5Cr-2K-XCe / Al (X = 0, 1, 2, 4, 8 parts by weight) catalyst of Example 1 of the present invention was placed in a quartz reactor, The reactor was heated from room temperature to 1000 ° C at 5 ° C per minute while injecting nitrogen (20 ml / m 2). As a result, the graph was detected by a thermal conductivity detector of gas chromatography, and a graph of a result of hydrogen-heating reduction according to the cerium oxide content is shown in FIG.
As shown in Fig. 3, 17.5Cr-2K-XCe / Al catalysts containing 0, 1, 2, 4, and 8 parts by weight of cerium oxide, based on 100 parts by weight of alumina, And it can be confirmed that the particle size of the chromium oxide is uniform and rarely occurs when the reduction of cerium oxide is less than 700 ° C.
(5) 0.05 g of 17.5Cr-2K-XCe / Al (X = 0, 1, 2, 4, 8 parts by weight) catalyst of Example 1 of the present invention was placed in a quartz reactor, The reactor was heated from room temperature to 1000 ° C at 5 ° C per minute while injecting nitrogen (20 ml / m 2). As a result, the graph was detected by the thermal conductivity detector of gas chromatography, and the lattice oxygen content calculated from the peak area of the hydrogen-heating reduction result graph according to the cerium oxide content is shown in Table 2 below.
As shown in Table 2, the lattice oxygen content of 17.5Cr-2K-XCe / Al catalysts containing 0, 1, 2, 4, and 8 parts by weight of cerium oxide was compared with 100 parts by weight of alumina. It can be seen that the lattice oxygen content is the largest when the amount of loading is 2 parts by weight, and the lattice oxygen content is decreased when the amount of cerium oxide is more than 2 parts by weight. Therefore, it can be confirmed that the 17.5Cr-2K-2Ce / Al catalyst can exhibit the highest activity in the dehydrogenation reaction of hydrocarbons.
EXPERIMENTAL EXAMPLE 2 Analysis of Dehydrogenation Process of Propane
The conversion of propane, the selectivity of propylene and the yield of propylene were analyzed according to the cerium oxide content of Example 2 of the present invention, and the results are shown in FIG. 4 and Table 3, respectively.
The conversion of propane, the selectivity of propylene and the yield of propylene in Example 2 were calculated by the following formulas 1 to 3, respectively.
[Formula 1]
[Formula 2]
[Formula 3]
The cerium oxide content of the 17.5Cr-2K-XCe / Al (X = 0, 1, 2, 4, 8 parts by weight) catalyst of Example 1 used in the dehydrogenation reaction of propane dehydrogenase of Example 2 of the present invention FIG. 4 is a graph showing changes in propane conversion, propylene selectivity, and propylene yield according to the present invention.
As shown in FIG. 4, since the reaction of the catalysts proceeded without the oxidizing agent, the conversion of propane decreased with time, but propylene selectivity was maintained.
The initial propane conversion, propylene selectivity, and propylene conversion of FIG. 4 are shown in Table 3 below.
As shown in Table 3, the conversion of propane and the degree of propylene selectivity were improved in the case of 17.5Cr-2K-2Ce / Al catalyst. As can be seen from the result of hydrogen-heating reduction, It is caused by the most. Also, the tendency of the propane conversion and the propylene yield showed the same tendency as the lattice oxygen content of Table 2, and the tendency of the propylene conversion and propylene yield was 17.5 Cr-2K-2Ce / Al> 17.5Cr-2K-1Ce / Al> 17.5Cr-2K / Cr-2K-4Ce / Al > 17.5Cr-2K-8Ce / Al.
Claims (10)
1 to 30 parts by weight of chromium oxide relative to 100 parts by weight of alumina,
0.1 to 10 parts by weight of potassium oxide and < RTI ID = 0.0 >
And 1 to 20 parts by weight of cerium oxide relative to 100 parts by weight of alumina.
Impregnating the alumina support of step 1 with a mixed solution comprising a chromium precursor, a potassium precursor and a cerium precursor (step 2);
The method for producing a catalyst for hydrocarbon dehydrogenation according to claim 1, comprising the step of drying and heat-treating the resultant obtained in step 2 (step 3).
Separating the catalyst used in the step 1 and the produced olefin and regenerating the separated catalyst (step 2); And
(Step 3) recycling the catalyst recovered in step 2 to the process of step 1,
The continuous reaction-regeneration and flow-type olefin production process wherein the above steps 1 to 3 are repeatedly carried out to continuously regenerate the catalyst and produce the olefin.
Preparing olefins from hydrocarbons using the catalyst pretreated in step 1 (step 2);
Separating the catalyst used in the step 2 and the produced olefin and regenerating the separated catalyst (step 3); And
(Step 4) of recycling the catalyst recovered in step 3 to the process of step 1,
The continuous reaction-regeneration and flow-type olefin production process wherein the above steps 1 to 4 are repeatedly carried out to continuously regenerate the catalyst and produce the olefin.
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| PCT/KR2015/008427 WO2017010600A1 (en) | 2015-07-10 | 2015-08-12 | Catalyst for preparing olefin through dehydrogenation of hydrocarbon and method for preparing same |
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| WO2018225952A1 (en) * | 2017-06-07 | 2018-12-13 | 에스케이가스 주식회사 | Olefin preparation method using circulating fluidized bed process |
| WO2018225951A1 (en) * | 2017-06-07 | 2018-12-13 | 에스케이가스 주식회사 | Olefin preparation method comprising reduction pretreatment |
| KR20180133696A (en) | 2017-06-07 | 2018-12-17 | 에스케이가스 주식회사 | Catalyst having enhanced stability, conversion ratio and selectivity for manufacturing olefin, and A method thereof |
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| KR102079768B1 (en) | 2018-05-08 | 2020-02-20 | 에스케이가스 주식회사 | A method for reducing nitrogen dioxide in the exhaust gas generated during an olefin production process |
| CN111468101B (en) * | 2019-01-24 | 2024-03-01 | 中国石油天然气股份有限公司 | Chromium catalyst and preparation method and application thereof |
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| WO2018225952A1 (en) * | 2017-06-07 | 2018-12-13 | 에스케이가스 주식회사 | Olefin preparation method using circulating fluidized bed process |
| WO2018225951A1 (en) * | 2017-06-07 | 2018-12-13 | 에스케이가스 주식회사 | Olefin preparation method comprising reduction pretreatment |
| KR20180133694A (en) * | 2017-06-07 | 2018-12-17 | 에스케이가스 주식회사 | A method for producing olefin comprising reduction pretreatment |
| KR20180133696A (en) | 2017-06-07 | 2018-12-17 | 에스케이가스 주식회사 | Catalyst having enhanced stability, conversion ratio and selectivity for manufacturing olefin, and A method thereof |
| KR20180133695A (en) * | 2017-06-07 | 2018-12-17 | 에스케이가스 주식회사 | A method for producing olefin by using circulating fluidization process |
| CN110678437A (en) * | 2017-06-07 | 2020-01-10 | Sk燃气株式会社 | Olefin production process including reduction pretreatment |
| CN110709372A (en) * | 2017-06-07 | 2020-01-17 | Sk燃气株式会社 | Process for the preparation of olefins using a circulating fluidized bed process |
| US10737990B2 (en) | 2017-06-07 | 2020-08-11 | Sk Gas Co., Ltd. | Olefin production method using circulating fluidized bed process |
| US10821432B2 (en) | 2017-06-07 | 2020-11-03 | Sk Gas Co., Ltd. | Olefin production method comprising reduction pretreatment |
| CN110709372B (en) * | 2017-06-07 | 2022-07-08 | Sk燃气株式会社 | Process for the preparation of olefins using a circulating fluidized bed process |
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