WO2020091415A1 - Method for directly synthesizing monocyclic aromatic compound from syngas - Google Patents

Method for directly synthesizing monocyclic aromatic compound from syngas Download PDF

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WO2020091415A1
WO2020091415A1 PCT/KR2019/014465 KR2019014465W WO2020091415A1 WO 2020091415 A1 WO2020091415 A1 WO 2020091415A1 KR 2019014465 W KR2019014465 W KR 2019014465W WO 2020091415 A1 WO2020091415 A1 WO 2020091415A1
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monocyclic aromatic
aromatic compound
catalyst
based catalyst
reaction
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French (fr)
Korean (ko)
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곽근재
박경아
강석창
전기원
이윤조
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한국화학연구원
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
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    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
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    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/04—Benzene
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C15/02—Monocyclic hydrocarbons
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    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/46—Iron group metals or copper
    • 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
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    • 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

Definitions

  • the present invention relates to a method for directly synthesizing a monocyclic aromatic compound from a synthesis gas, and more specifically, synthesis of a monocyclic aromatic compound using a synthesis gas as a raw material and directly producing a high value-added monocyclic aromatic compound in one-step. It's about how.
  • the Fischer-Tropsch (FT) synthesis process which is a core process of GTL technology, is a process for producing hydrocarbons from synthesis gas produced through a reforming reaction of natural gas.
  • FT synthesis process hydrocarbons discharged through the FT synthesis process have a wide carbon number range, so additional separation and upgrading processes are required for product production. Accordingly, research is being actively conducted to synthesize hydrocarbons in a relatively narrow carbon number range by adjusting the conditions of the FT synthesis process in order to simplify the GTL process and produce an efficient product.
  • iron-based catalysts and cobalt-based catalysts are mainly used.
  • iron-based catalysts were mainly used, but recently, cobalt-based catalysts are mainly used.
  • the molar ratio of H 2 / CO as the composition ratio of the synthesis gas used as a raw material has to be closely matched to 2, so it is not only difficult to meet the operating conditions, but also for the use of carbon dioxide contained in the synthesis gas. Because it is not considered, the thermal efficiency and carbon efficiency of the entire process are relatively low, and secondary environmental problems may occur.
  • carbon dioxide can be converted to hydrocarbon by a water gas conversion reaction, so it is an eco-friendly process with relatively high thermal efficiency and carbon efficiency (Patent Document 1).
  • Patent Document 2 proposes a method for producing from a polycyclic aromatic compound contained in light cycle oil (LCO) or the like using a zeolite catalyst.
  • LCO light cycle oil
  • Patent Document 2 it can be produced only in a mixed fuel oil, the yield of the monocyclic aromatic compound is not high, and catalyst deactivation by carbon deposition easily occurs.
  • the present inventors use synthetic gas as a raw material to directly synthesize a monocyclic aromatic compound and a long-chain olefin compound by the Fischer-Tropsch (FT) synthesis process of the C1-C15 short-chain hydrocarbon production step and the prepared short-chain hydrocarbon.
  • FT Fischer-Tropsch
  • a synthesis method including a dehydrogenation step has been disclosed (see Patent Document 3)
  • the composition and temperature and pressure conditions of the catalyst used in the short-chain hydrocarbon production step and the dehydrogenation step must be separately controlled, and the deactivation rate of the catalyst is
  • the design and process of the two processes are different, and there is a problem that a separation and purification process with a long-chain olefin compound is necessary in order to obtain a monocyclic aromatic compound.
  • Patent Document 1 Korean Registered Patent No. 10-1418911 (Announcement date: 2014.07.14)
  • Patent Document 2 Korean Patent Publication No. 10-2014-0027082 (Publication Date: 2011.12.28)
  • Patent Document 3 Korean Registered Patent No. 10-1600430 (Publication date: 2016.03.07)
  • the main object of the present invention is to solve the above-mentioned problems, and provides a method for synthesizing a monocyclic aromatic compound that can produce a monocyclic aromatic compound simply and efficiently in a one-step process using synthetic gas as a raw material. Is doing.
  • an embodiment of the present invention comprises the steps of preparing a monocyclic aromatic compound by reacting a synthesis gas in the presence of a mixed catalyst in which an iron-based catalyst and a crystalline aluminosilicate-based catalyst are mixed.
  • a method for synthesizing an aromatic compound is provided.
  • the reaction may be characterized in that it is carried out at 1 bar to 25 bar at 250 ° C to 400 ° C.
  • the reaction may be characterized in that it is carried out at 10 bar ⁇ 20 bar at 340 °C ⁇ 380 °C.
  • the synthesis gas may be characterized in that the molar ratio of H 2 / CO is in the range of 0.1 to 3.
  • the composite catalyst may be characterized in that the weight ratio of the iron-based catalyst and the crystalline aluminosilicate-based catalyst is 1: 0.1 to 1: 10.
  • the iron-based catalyst is copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), sodium (Na), chromium ( Cr), silicon (Si) and potassium (K) may be characterized in that it further contains at least one co-catalyst selected from the group consisting of.
  • the crystalline aluminosilicate-based catalyst is selected from the group consisting of ZSM-5, H-beta, L-zeolite, Y-zeolite, SAPO-34, MCM-22 and H-USY It can be characterized by one or more.
  • the crystalline aluminosilicate-based catalyst is gallium (Ga), zinc (Zn), platinum (Pt), palladium (Pd), tungsten (W), cobalt (Co) and iron ( Fe) may be characterized in that it further contains at least one co-catalyst selected from the group consisting of.
  • the monocyclic aromatic compound may be characterized in that it comprises at least one compound selected from the group consisting of benzene, toluene, ethylbenzene and xylene.
  • the present invention in the production of a monocyclic aromatic compound, it is possible to simplify the process by a one-step process with specific reaction conditions, and because the operation is simple and the process time is fast, not only mass production of the monocyclic aromatic compound is possible, but also natural gas, coal,
  • synthetic gas which can be obtained from various raw materials such as petroleum refining compounds, as a raw material, the utilization of technology is high, and direct monocyclic aromatic compounds can be produced in high yield, thereby solving the problem of supplying high value-added monocyclic aromatic compounds.
  • FIG. 1 is a schematic diagram schematically showing a method for directly synthesizing a monocyclic aromatic compound from a synthesis gas according to the present invention.
  • the present invention relates to a method for synthesizing a monocyclic aromatic compound, comprising the step of preparing a monocyclic aromatic compound by reacting a synthesis gas in the presence of a mixed catalyst in which an iron-based catalyst and a crystalline aluminosilicate-based catalyst are mixed.
  • the method for synthesizing the monocyclic aromatic compound of the present invention uses a synthetic gas as a raw material to prepare a monocyclic aromatic compound in a single step process under a specific reaction condition, and an iron-based catalyst 151 and crystals as shown in FIG.
  • Synthetic gas CO and H 2
  • a monocyclic aromatic compound is prepared by the Fischer-Tropsch reaction of syngas in the presence of the mixed catalyst 150 in which the catalyst is mixed and the dehydrogenation reaction of hydrocarbons formed in the Fischer-Tropsch reaction.
  • Synthesis gas used as a raw material in the present invention include hydrogen (H 2) and a and containing carbon monoxide (CO), H 2 / CO molar ratio of 0.1 to 3 range, preferably at a molar ratio of H 2 / CO of 1 - 2 Phosphorus syngas is used. If, when the molar ratio of H 2 / CO of the synthesis gas is less than 0.1, the carbon deposition rate increases, the catalyst life may be shortened, the yield of aromatic compounds may decrease, and the molar ratio of H 2 / CO exceeds 3 When the hydrogenation (hydrogenation) is promoted, the selectivity of unnecessary methane and short-chain paraffins increases, which may eventually lower the yield of monocyclic aromatic compounds.
  • the synthesis gas may be produced through a reforming process of natural gas, and methods for reforming the natural gas may include a steam reforming method, a carbon dioxide reforming method, a complex reforming method, and a partial oxidation method. Particularly preferred is to produce and use the syngas by a composite reforming method capable of controlling the composition of the syngas.
  • the composite catalyst applied to the synthesis reaction of the monocyclic aromatic compound from the synthesis gas is a composite catalyst in which an iron-based catalyst and a crystalline aluminosilicate-based catalyst are mixed, and the mixture of the iron-based catalyst and a crystalline aluminosilicate-based catalyst is laminated It can be physically mixed by a layer by layer method, a simple mixing method, or the like.
  • the mixing ratio of the composite catalyst may be a composite catalyst in which the weight ratio of the iron-based catalyst and the crystalline aluminosilicate-based catalyst is 1: 0.1 to 1:10, preferably 1: 2 to 1: 4. If, in the composite catalyst, the weight ratio of the crystalline aluminosilicate-based catalyst to the iron-based catalyst is less than 0.1, the Fischer-Tropsch synthesis reaction occurs predominantly, the yield of aromatic compounds decreases, and the yield of short-chain olefins increases. When the weight ratio of the crystalline aluminosilicate-based catalyst to the iron-based catalyst exceeds 10, carbon deposition may occur due to excessive cracking and dehydrogenation reaction, resulting in a decrease in the life of the catalyst.
  • the iron-based catalyst may be a conventional catalyst used in the Fischer-Tropsch synthesis process, wherein the iron-based catalyst is copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), if necessary. It may further include one or more cocatalysts selected from the group consisting of zinc (Zn), aluminum (Al), sodium (Na), chromium (Cr), silicon (Si), and potassium (K).
  • the crystalline aluminosilicate-based catalyst may be one or more selected from the group consisting of ZSM-5, H-beta, L-zeolite, Y-zeolite, SAPO-34, MCM-22 and H-USY,
  • a crystalline aluminosilicate-based catalyst having a Si / Al molar ratio of 10 to 150, preferably 15 to 25, may be used. If the molar ratio of Si / Al is less than 10, the dehydrogenation reaction proceeds violently, which is not preferable because the productivity of the polycyclic aromatic compound rather than the monocyclic aromatic compound is high. On the other hand, when the molar ratio of Si / Al exceeds 150, it is not preferable because the chain growth reaction is dominant and the productivity of the monocyclic aromatic compound decreases.
  • the crystalline aluminosilicate-based catalyst is a crystalline porous body and includes an intermediate pore of 10 nm or less, and a micropore size of 1 to 8 mm 2 is used. At this time, if the pore size of the crystalline porous body does not satisfy the above range, it is not preferable because the productivity of the monocyclic aromatic compound decreases.
  • the crystalline aluminosilicate-based catalyst may be used alone, but the crystalline aluminosilicate-based catalyst may be gallium (Ga), zinc (Zn), platinum (Pt), palladium (Pd), tungsten as required. (W), cobalt (Co) and iron (Fe) may further include one or more cocatalysts selected from the group consisting of.
  • the weight ratio of A / Al is preferably maintained at 0.01 to 2.5.
  • the weight ratio of the cocatalyst metal element (A) based on the aluminum atom is included to be 0.1 to 1.
  • the reactor 100 When the synthesis gas flows into the reactor 100 filled with the complex catalyst 150 as described above, hydrocarbons are formed by Fischer-Tropsch reaction of the synthesis gas in the reactor, and the formed hydrocarbons are monocyclic aromatic by dehydrogenation reaction.
  • the compound is prepared.
  • the reactor 100 may be applied without limitation to the reactor surface that can be used in a conventional Fischer-Tropsch synthesis process such as a slurry bed reactor, a fixed bed reactor, a fluidized bed reactor, and the like.
  • reaction pressure is maintained at a temperature lower than 340 ° C. and the reaction pressure is higher than 10 bar.
  • the reaction temperature high at 400 ° C. or higher while maintaining a reaction pressure as low as 5 bar or less.
  • the reaction conditions of the present invention can proceed to a pressure range of 1 bar to 25 bar in a temperature range of 250 ° C to 400 ° C, preferably a pressure range of 10 bar to 20 bar in a temperature range of 340 ° C to 380 ° C.
  • the product produced by such a reaction may include a monocyclic aromatic compound, which is an aromatic compound having one ring, such as benzene, toluene, ethylbenzene, and xylene, and light hydrocarbons (C1 to C4) as reaction by-products.
  • a separation / purification step through a gas / liquid separation device or the like can be added to the rear stage to separate gaseous light hydrocarbons (C1 to C4) and liquid monocyclic aromatic compounds.
  • the distillation temperature of the gas / liquid separation device is preferably -5 ° C to 5 ° C. If the temperature of the separator is less than -5 ° C, it is not preferable because water, a by-product of the reaction, may be frozen, and the separator may be damaged. If it exceeds 5 ° C, light hydrocarbons (C1 to C4) and liquid hydrocarbons (C5 +) Is not preferred because of insufficient separation.
  • the light hydrocarbons of C1 to C4 separated through the gas / liquid separation device may be recycled to a reforming reactor for syngas production.
  • Example 1-1 The reaction was carried out in the same manner as in Example 1-1, but as a catalyst, 0.3 g of an iron-based catalyst having a composition ratio of 100Fe-6Cu-16Al-4K was charged instead of a composite catalyst, and the reaction was carried out under the conditions in Table 1 below.
  • Table 2 shows the results of analyzing the composition of the product.
  • Example 1-1 100Fe-6Cu-16Al-4K + HZSM-5 1) 300 20
  • Example 1-2 100Fe-6Cu-16Al-4K + HZSM-5 1) 320 20
  • Example 1-3 100Fe-6Cu-16Al-4K + HZSM-5 1) 340 20
  • Example 1-4 100Fe-6Cu-16Al-4K + HZSM-5 1) 360 20
  • Example 1-5 100Fe-6Cu-16Al-4K + HZSM-5 1)
  • Example 1-6 100Fe-6Cu-16Al-4K + HZSM-5 1) 340
  • One Example 1-7 100Fe-6Cu-16Al-4K + HZSM-5 1) 340 5
  • Example 1-8 100Fe-6Cu-16Al-4K + HZSM-5 1) 340 10
  • Example 1-1 98.7 31.8 11.4 44.1 0.43 44.5 10.1
  • Example 1-2 98.4 30.7 14.1 46.9 0.44 39.0 10.0
  • Example 1-3 98.0 29.6 18.0 48.1 0.69 33.9 13.7
  • Example 1-4 97.4 31.0 20.9 46.9 0.78 32.2 14.1
  • Example 1-5 96.8 29.8 26.4 46.5 0.99 27.2 17.5
  • Example 1-6 7.5 55.0 28.4 22.5 48 49.1 7.9
  • Example 1-7 96.6 35.5 26.9 43.0 2.0 30.1 16.9
  • Example 1-8 97.6 32.1 21.4 46.7 0.95 31.9 18.3 Comparative Example 1-1 98.3 29.8 10.5 31.9 74.3 57.6 - Comparative Example 1-2 98.0 31.0 12.9 31.3 76.6 55.8 - 2)
  • BTEX BTEX:
  • the synthesis reaction was carried out by varying the H 2 / CO molar ratio of the synthesis gas used as a raw material under the same conditions as in Example 1-8, and the results are shown in Table 3 below.
  • Example 1-8 Under the same conditions as in Example 1-8, the catalytic conditions were changed to the conditions in Table 4 below, and the synthesis reaction was performed, and the results are shown in Table 5 below.

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Abstract

The present invention relates to a method for directly synthesizing a monocyclic aromatic compound from syngas and, more specifically, to a method for directly synthesizing a monocyclic aromatic compound from syngas, the method enabling a process to be simplified into a one-step process of a specific reaction condition when preparing a monocyclic aromatic compound, enabling mass production of a monocyclic aromatic compound by having both a simple operation and a short processing time, and enabling direct production of a monocyclic aromatic compound in a high yield by using syngas as a material, thereby enabling a supply problem of a high value-added monocyclic aromatic compound to be resolved.

Description

합성가스로부터 단환 방향족 화합물의 직접 합성방법Method for directly synthesizing monocyclic aromatic compounds from syngas
본 발명은 합성가스로부터 단환 방향족 화합물의 직접 합성방법에 관한 것으로, 보다 상세하게는 합성가스를 원료로 사용하여 고부가가치의 단환 방향족 화합물을 원스텝(one-step)으로 직접 제조하는 단환 방향족 화합물의 합성방법에 관한 것이다.The present invention relates to a method for directly synthesizing a monocyclic aromatic compound from a synthesis gas, and more specifically, synthesis of a monocyclic aromatic compound using a synthesis gas as a raw material and directly producing a high value-added monocyclic aromatic compound in one-step. It's about how.
GTL 기술의 핵심 공정인 피셔-트롭쉬(FT) 합성공정은 천연가스의 개질 반응을 통해 제조된 합성가스로부터 탄화수소를 제조하는 공정이다. 그러나 FT 합성공정을 통해 배출되는 탄화수소는 탄소수 범위가 광범위하므로, 제품생산을 위해서는 추가적인 분리 및 업그레이딩 공정이 필요하다. 이에, GTL 공정의 간소화 및 효율적인 제품생산을 위하여 FT 합성공정 조건을 조절하여, 비교적 좁은 탄소수 범위의 탄화수소를 합성하고자 하는 연구가 활발하게 진행되고 있다.The Fischer-Tropsch (FT) synthesis process, which is a core process of GTL technology, is a process for producing hydrocarbons from synthesis gas produced through a reforming reaction of natural gas. However, hydrocarbons discharged through the FT synthesis process have a wide carbon number range, so additional separation and upgrading processes are required for product production. Accordingly, research is being actively conducted to synthesize hydrocarbons in a relatively narrow carbon number range by adjusting the conditions of the FT synthesis process in order to simplify the GTL process and produce an efficient product.
FT 합성공정에는 주로 철계 촉매와 코발트계 촉매가 사용된다. 기술 개발 초기에는 철계 촉매가 주로 사용되었으나, 최근에는 코발트계 촉매가 주로 이용되고 있다. 하지만, 코발트계 촉매를 이용한 FT 합성공정에서는 원료로 사용되는 합성가스의 조성비로서 H2/CO의 몰비를 2에 가깝게 맞추어야 하므로 운전 조건을 맞추기가 까다로울 뿐만 아니라, 합성가스 내에 포함된 이산화탄소의 이용에 대해서는 고려치 않고 있기 때문에 공정 전체의 열효율 및 탄소효율이 비교적 낮으며 이차적인 환경문제가 발생할 수 있다. 이에 반하여 철계 촉매를 이용한 FT 합성공정에서는 수성가스전환반응에 의하여 이산화탄소를 탄화수소로 전환할 수 있기 때문에 열효율 및 탄소효율이 비교적 높은 친환경 공정이다(특허 문헌 1).In the FT synthesis process, iron-based catalysts and cobalt-based catalysts are mainly used. In the early stage of technology development, iron-based catalysts were mainly used, but recently, cobalt-based catalysts are mainly used. However, in the FT synthesis process using a cobalt-based catalyst, the molar ratio of H 2 / CO as the composition ratio of the synthesis gas used as a raw material has to be closely matched to 2, so it is not only difficult to meet the operating conditions, but also for the use of carbon dioxide contained in the synthesis gas. Because it is not considered, the thermal efficiency and carbon efficiency of the entire process are relatively low, and secondary environmental problems may occur. On the other hand, in the FT synthesis process using an iron-based catalyst, carbon dioxide can be converted to hydrocarbon by a water gas conversion reaction, so it is an eco-friendly process with relatively high thermal efficiency and carbon efficiency (Patent Document 1).
한편, 벤젠, 톨루엔, 자일렌, 에틸벤젠 등의 단환 방향족 화합물은 합성섬유, 각종 플라스틱, 휘발유 첨가제 등 석유화학제품의 기초 원료로 이용되고 있다. 종래 방법에서는 단환 방향족 화합물은 주로 혼합 연료유로부터 제조되고 있다. 상기 방향족 화합물의 제조방법으로서 특허문헌 2에는 제올라이트 촉매를 사용하여 경질 사이클유(LCO) 등에 포함된 다환 방향족 화합물로부터 제조하는 방법이 제안되어 있다.Meanwhile, monocyclic aromatic compounds such as benzene, toluene, xylene, and ethylbenzene are used as basic raw materials for petrochemical products such as synthetic fibers, various plastics, and gasoline additives. In the conventional method, monocyclic aromatic compounds are mainly produced from mixed fuel oil. As a method for producing the aromatic compound, Patent Document 2 proposes a method for producing from a polycyclic aromatic compound contained in light cycle oil (LCO) or the like using a zeolite catalyst.
그러나 상기 특허문헌 2에서 제시한 방법에 의하면 혼합 연료유에서만 제조 가능하고, 단환 방향족 화합물의 수율이 높지 않으며, 탄소 침적에 의한 촉매 비활성화가 쉽게 발생되는 문제가 있었다.However, according to the method proposed in Patent Document 2, it can be produced only in a mixed fuel oil, the yield of the monocyclic aromatic compound is not high, and catalyst deactivation by carbon deposition easily occurs.
이에, 본 발명자는 합성가스를 원료로 사용하여 단환 방향족 화합물과 장쇄 올레핀 화합물을 직접 합성하기 위해 피셔-트롭쉬(FT) 합성공정에 의한 C1 ~ C15의 단쇄 탄화수소의 제조 단계와 제조된 단쇄 탄화수소의 탈수소화 단계를 포함하는 합성방법을 개시한 바 있으나(특허문헌 3 참조), 단쇄 탄화수소 제조단계와 탈수소화 단계에 사용되는 촉매의 조성과 온도 및 압력 조건을 별도로 제어해야 하며, 촉매의 비활성화 속도가 달라 두 공정의 설계 및 과정이 복잡하고, 단환 방향족 화합물을 얻기 위해서는 장쇄 올레핀 화합물과의 분리정제 공정이 필수적으로 필요하다는 문제점이 있었다.Thus, the present inventors use synthetic gas as a raw material to directly synthesize a monocyclic aromatic compound and a long-chain olefin compound by the Fischer-Tropsch (FT) synthesis process of the C1-C15 short-chain hydrocarbon production step and the prepared short-chain hydrocarbon. Although a synthesis method including a dehydrogenation step has been disclosed (see Patent Document 3), the composition and temperature and pressure conditions of the catalyst used in the short-chain hydrocarbon production step and the dehydrogenation step must be separately controlled, and the deactivation rate of the catalyst is The design and process of the two processes are different, and there is a problem that a separation and purification process with a long-chain olefin compound is necessary in order to obtain a monocyclic aromatic compound.
[선행기술문헌][Advanced technical literature]
[특허문헌][Patent Document]
(특허문헌 1) 한국등록특허 제10-1418911호(공고일 : 2014.07.14) (Patent Document 1) Korean Registered Patent No. 10-1418911 (Announcement date: 2014.07.14)
(특허문헌 2) 한국공개특허 제10-2014-0027082호(공개일 : 2011.12.28)(Patent Document 2) Korean Patent Publication No. 10-2014-0027082 (Publication Date: 2011.12.28)
(특허문헌 3) 한국등록특허 제10-1600430호(공고일 : 2016.03.07)(Patent Document 3) Korean Registered Patent No. 10-1600430 (Publication date: 2016.03.07)
본 발명의 주된 목적은 상술한 문제점을 해결하기 위한 것으로서, 합성가스를 원료로 사용하여 원스텝(one-step) 공정으로 단환 방향족 화합물을 간단하면서 효율적으로 제조할 수 있는 단환 방향족 화합물의 합성방법을 제공하는데 있다.The main object of the present invention is to solve the above-mentioned problems, and provides a method for synthesizing a monocyclic aromatic compound that can produce a monocyclic aromatic compound simply and efficiently in a one-step process using synthetic gas as a raw material. Is doing.
상기와 같은 목적을 달성하기 위하여, 본 발명의 일 구현예는 철계 촉매 및 결정성 알루미노실리케이트계 촉매가 혼합된 복합촉매 존재하에 합성가스를 반응시켜 단환 방향족 화합물을 제조하는 단계를 포함하는, 단환 방향족 화합물의 합성방법을 제공한다.In order to achieve the above object, an embodiment of the present invention comprises the steps of preparing a monocyclic aromatic compound by reacting a synthesis gas in the presence of a mixed catalyst in which an iron-based catalyst and a crystalline aluminosilicate-based catalyst are mixed. A method for synthesizing an aromatic compound is provided.
본 발명의 바람직한 일 구현예에서, 상기 반응은 250 ℃ ~ 400 ℃에서 1 bar ~ 25 bar로 수행하는 것을 특징으로 할 수 있다.In a preferred embodiment of the present invention, the reaction may be characterized in that it is carried out at 1 bar to 25 bar at 250 ° C to 400 ° C.
본 발명의 바람직한 일 구현예에서, 상기 반응은 340 ℃ ~ 380 ℃에서 10 bar ~ 20 bar로 수행하는 것을 특징으로 할 수 있다.In a preferred embodiment of the present invention, the reaction may be characterized in that it is carried out at 10 bar ~ 20 bar at 340 ℃ ~ 380 ℃.
본 발명의 바람직한 일 구현예에서, 상기 합성가스는 H2/CO의 몰비가 0.1 ~ 3 범위인 것을 특징으로 할 수 있다.In a preferred embodiment of the present invention, the synthesis gas may be characterized in that the molar ratio of H 2 / CO is in the range of 0.1 to 3.
본 발명의 바람직한 일 구현예에서, 상기 복합촉매는 철계 촉매 및 결정성 알루미노실리케이트계 촉매의 중량비가 1 : 0.1 내지 1 : 10인 것을 특징으로 할 수 있다.In a preferred embodiment of the present invention, the composite catalyst may be characterized in that the weight ratio of the iron-based catalyst and the crystalline aluminosilicate-based catalyst is 1: 0.1 to 1: 10.
본 발명의 바람직한 일 구현예에서, 상기 철계 촉매는 구리(Cu), 망간(Mn), 코발트(Co), 니켈(Ni), 아연(Zn), 알루미늄(Al), 나트륨(Na), 크롬(Cr), 실리콘(Si) 및 칼륨(K)으로 구성된 군에서 선택되는 1종 이상의 조촉매가 더 함유된 것을 특징으로 할 수 있다.In a preferred embodiment of the present invention, the iron-based catalyst is copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), sodium (Na), chromium ( Cr), silicon (Si) and potassium (K) may be characterized in that it further contains at least one co-catalyst selected from the group consisting of.
본 발명의 바람직한 일 구현예에서, 상기 결정성 알루미노실리케이트계 촉매는 ZSM-5, H-beta, L-zeolite, Y-zeolite, SAPO-34, MCM-22 및 H-USY로 구성된 군에서 선택되는 1 종 이상인 것을 특징으로 할 수 있다.In a preferred embodiment of the present invention, the crystalline aluminosilicate-based catalyst is selected from the group consisting of ZSM-5, H-beta, L-zeolite, Y-zeolite, SAPO-34, MCM-22 and H-USY It can be characterized by one or more.
본 발명의 바람직한 일 구현예에서, 상기 결정성 알루미노실리케이트계 촉매는 갈륨(Ga), 아연(Zn), 백금(Pt), 팔라듐(Pd), 텅스텐(W), 코발트(Co) 및 철(Fe)로 구성된 군에서 선택되는 1종 이상의 조촉매가 더 함유된 것을 특징으로 할 수 있다.In one preferred embodiment of the present invention, the crystalline aluminosilicate-based catalyst is gallium (Ga), zinc (Zn), platinum (Pt), palladium (Pd), tungsten (W), cobalt (Co) and iron ( Fe) may be characterized in that it further contains at least one co-catalyst selected from the group consisting of.
본 발명의 바람직한 일 구현예에서, 상기 단환 방향족 화합물은 벤젠, 톨루엔, 에틸벤젠 및 자일렌으로 구성된 군에서 선택되는 1종 이상의 화합물을 포함하는 것을 특징으로 할 수 있다. In a preferred embodiment of the present invention, the monocyclic aromatic compound may be characterized in that it comprises at least one compound selected from the group consisting of benzene, toluene, ethylbenzene and xylene.
본 발명에 따르면, 단환 방향족 화합물의 제조시 특정 반응조건의 원스텝 공정으로 공정의 단순화가 가능하고, 조작이 간단한 동시에 공정 시간이 빠르기 때문에 단환 방향족 화합물의 대량 생산이 가능할 뿐만 아니라, 천연가스, 석탄, 석유 정제화합물 등 다양한 원료로부터 얻어질 수 있는 합성가스를 원료로 사용함으로써, 기술의 활용도가 높으며, 직접 단환 방향족 화합물을 고수율로 생산할 수 있어 고부가가치의 단환 방향족 화합물의 공급 문제를 해결할 수 있는 효과가 있다.According to the present invention, in the production of a monocyclic aromatic compound, it is possible to simplify the process by a one-step process with specific reaction conditions, and because the operation is simple and the process time is fast, not only mass production of the monocyclic aromatic compound is possible, but also natural gas, coal, By using synthetic gas, which can be obtained from various raw materials such as petroleum refining compounds, as a raw material, the utilization of technology is high, and direct monocyclic aromatic compounds can be produced in high yield, thereby solving the problem of supplying high value-added monocyclic aromatic compounds. There is.
도 1은 본 발명에 따른 합성가스로부터 단환 방향족 화합물의 직접 합성방법을 개략적으로 도시한 개략도이다.1 is a schematic diagram schematically showing a method for directly synthesizing a monocyclic aromatic compound from a synthesis gas according to the present invention.
[부호의 설명][Description of codes]
100 : 반응기100: reactor
150 : 복합촉매150: complex catalyst
151 : 철계 촉매151: iron-based catalyst
152 : 결정성 알루미노실리케이트계 촉매152: crystalline aluminosilicate-based catalyst
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 가진다. 일반적으로, 본 명세서에서 사용된 명명법 은 본 기술분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.
본원 명세서 전체에서 어떤 부분이 어떤 구성 요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다. When a certain part of the present specification “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.
본 발명은 철계 촉매 및 결정성 알루미노실리케이트계 촉매가 혼합된 복합촉매 존재하에 합성가스를 반응시켜 단환 방향족 화합물을 제조하는 단계를 포함하는, 단환 방향족 화합물의 합성방법에 관한 것이다.The present invention relates to a method for synthesizing a monocyclic aromatic compound, comprising the step of preparing a monocyclic aromatic compound by reacting a synthesis gas in the presence of a mixed catalyst in which an iron-based catalyst and a crystalline aluminosilicate-based catalyst are mixed.
보다 구체적으로, 본 발명의 단환 방향족 화합물의 합성방법은 합성가스를 원료로 사용하여 특정 반응 조건의 단일 단계 공정으로 단환 방향족 화합물을 제조하는 것으로, 도 1에 나타난 바와 같이 철계 촉매(151) 및 결정성 알루미노실리케이트계 촉매(152)가 혼합된 복합촉매(150)를 장입한 반응기(100) 내로 합성가스(CO 및 H2)를 유입시키고, 유입된 합성가스는 철계 촉매 및 결정성 알루미노실리케이트계 촉매가 혼합된 복합촉매(150) 존재하에 합성가스의 피셔-트롭쉬 반응과, 피셔-트롭쉬 반응에서 형성된 탄화수소의 탈수소화 반응으로 단환 방향족 화합물을 제조한다.More specifically, the method for synthesizing the monocyclic aromatic compound of the present invention uses a synthetic gas as a raw material to prepare a monocyclic aromatic compound in a single step process under a specific reaction condition, and an iron-based catalyst 151 and crystals as shown in FIG. Synthetic gas (CO and H 2 ) is introduced into the reactor 100 in which the composite catalyst 150 in which the aluminosilicate-based catalyst 152 is mixed is charged, and the introduced synthetic gas is an iron-based catalyst and crystalline aluminosilicate. A monocyclic aromatic compound is prepared by the Fischer-Tropsch reaction of syngas in the presence of the mixed catalyst 150 in which the catalyst is mixed and the dehydrogenation reaction of hydrocarbons formed in the Fischer-Tropsch reaction.
본 발명에서 원료로 사용하는 합성가스는 수소(H2) 및 일산화탄소(CO)를 함유하고 있으며, H2/CO의 몰비가 0.1 ~ 3 범위, 바람직하게는 H2/CO의 몰비가 1 ~ 2인 합성가스를 사용한다. 만일, 상기 합성가스의 H2/CO의 몰비가 0.1 미만일 경우, 탄소 침적율이 증가하여 촉매 수명이 짧아질 수 있고, 방향족 화합물의 수율이 줄어들 수 있으며, H2/CO의 몰비가 3을 초과할 경우에는 수소화(hydrogenation)가 촉진됨에 따라 불필요한 메탄 및 단쇄 파라핀의 선택도가 증가하게 되어 결국엔 단환 방향족 화합물의 수율을 낮추는 원인이 될 수 있다.Synthesis gas used as a raw material in the present invention include hydrogen (H 2) and a and containing carbon monoxide (CO), H 2 / CO molar ratio of 0.1 to 3 range, preferably at a molar ratio of H 2 / CO of 1 - 2 Phosphorus syngas is used. If, when the molar ratio of H 2 / CO of the synthesis gas is less than 0.1, the carbon deposition rate increases, the catalyst life may be shortened, the yield of aromatic compounds may decrease, and the molar ratio of H 2 / CO exceeds 3 When the hydrogenation (hydrogenation) is promoted, the selectivity of unnecessary methane and short-chain paraffins increases, which may eventually lower the yield of monocyclic aromatic compounds.
또한, 상기 합성가스는 천연가스의 개질 공정을 통해 제조될 수 있으며, 상기 천연가스의 개질을 위한 방법으로는 수증기 개질법, 이산화탄소 개질법, 복합 개질법, 부분 산화법 등이 포함될 수 있다. 특히 좋기로는 합성가스의 조성 조절이 가능한 복합 개질법에 의해 합성가스를 제조하여 사용하는 것이다.In addition, the synthesis gas may be produced through a reforming process of natural gas, and methods for reforming the natural gas may include a steam reforming method, a carbon dioxide reforming method, a complex reforming method, and a partial oxidation method. Particularly preferred is to produce and use the syngas by a composite reforming method capable of controlling the composition of the syngas.
한편, 상기 합성가스로부터 단환 방향족 화합물의 합성 반응에 적용되는 복합촉매는 철계 촉매 및 결정성 알루미노실리케이트계 촉매가 혼합된 복합촉매로, 상기 철계 촉매 및 결정성 알루미노실리케이트계 촉매의 혼합은 적층혼합(layer by layer) 방법, 단순혼합(mixing) 방법 등으로 물리적으로 혼합시킬 수 있다.On the other hand, the composite catalyst applied to the synthesis reaction of the monocyclic aromatic compound from the synthesis gas is a composite catalyst in which an iron-based catalyst and a crystalline aluminosilicate-based catalyst are mixed, and the mixture of the iron-based catalyst and a crystalline aluminosilicate-based catalyst is laminated It can be physically mixed by a layer by layer method, a simple mixing method, or the like.
상기 복합촉매의 혼합비율은 철계 촉매 및 결정성 알루미노실리케이트계 촉매의 중량비가 1 : 0.1 내지 1 : 10, 바람직하게 1 : 2 내지 1 : 4로 혼합된 복합촉매일 수 있다. 만일, 상기 복합촉매에 있어서, 철계 촉매에 대한 결정성 알루미노실리케이트계 촉매 중량비가 0.1 미만일 경우, 피셔-트롭쉬 합성반응이 우세하게 일어나 방향족 화합물의 수율은 감소하고, 단쇄 올레핀의 수율이 증가하게 되며, 철계 촉매에 대한 결정성 알루미노실리케이트계 촉매 중량비가 10을 초과할 경우에는 과도한 크래킹과 탈수소화 반응으로 인해 탄소 침적이 일어나 촉매의 수명이 저하되는 문제가 발생될 수 있다. The mixing ratio of the composite catalyst may be a composite catalyst in which the weight ratio of the iron-based catalyst and the crystalline aluminosilicate-based catalyst is 1: 0.1 to 1:10, preferably 1: 2 to 1: 4. If, in the composite catalyst, the weight ratio of the crystalline aluminosilicate-based catalyst to the iron-based catalyst is less than 0.1, the Fischer-Tropsch synthesis reaction occurs predominantly, the yield of aromatic compounds decreases, and the yield of short-chain olefins increases. When the weight ratio of the crystalline aluminosilicate-based catalyst to the iron-based catalyst exceeds 10, carbon deposition may occur due to excessive cracking and dehydrogenation reaction, resulting in a decrease in the life of the catalyst.
이때, 상기 철계 촉매로는 피셔-트롭쉬 합성공정에서 사용되는 통상의 촉매일 수 있으며, 상기 철계 촉매는 필요에 따라 구리(Cu), 망간(Mn), 코발트(Co), 니켈(Ni), 아연(Zn), 알루미늄(Al), 나트륨(Na), 크롬(Cr), 실리콘(Si) 및 칼륨(K)으로 구성된 군에서 선택된 1종 이상의 조촉매를 더 포함할 수 있다.At this time, the iron-based catalyst may be a conventional catalyst used in the Fischer-Tropsch synthesis process, wherein the iron-based catalyst is copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), if necessary. It may further include one or more cocatalysts selected from the group consisting of zinc (Zn), aluminum (Al), sodium (Na), chromium (Cr), silicon (Si), and potassium (K).
또한, 상기 결정성 알루미노실리케이트계 촉매는 ZSM-5, H-beta, L-zeolite, Y-zeolite, SAPO-34, MCM-22 및 H-USY로 구성된 군에서 선택되는 1 종 이상일 수 있으며, 바람직하게는 Si/Al의 몰비가 10 ~ 150, 바람직하게는 15 ~ 25인 결정성 알루미노실리케이트계 촉매를 사용할 수 있다. 만일, 상기 Si/Al의 몰비가 10 미만이면 탈수소화 반응이 격렬하게 진행되어 단환 방향족 화합물이 아닌 다환 방향족 화합물의 생산성이 높기 때문에 바람직하지 않다. 반면에, Si/Al의 몰비가 150을 초과하면 사슬 성장반응이 우세하여 단환 방향족 화합물의 생산성이 저하되기 때문에 바람직하지 않다.In addition, the crystalline aluminosilicate-based catalyst may be one or more selected from the group consisting of ZSM-5, H-beta, L-zeolite, Y-zeolite, SAPO-34, MCM-22 and H-USY, Preferably, a crystalline aluminosilicate-based catalyst having a Si / Al molar ratio of 10 to 150, preferably 15 to 25, may be used. If the molar ratio of Si / Al is less than 10, the dehydrogenation reaction proceeds violently, which is not preferable because the productivity of the polycyclic aromatic compound rather than the monocyclic aromatic compound is high. On the other hand, when the molar ratio of Si / Al exceeds 150, it is not preferable because the chain growth reaction is dominant and the productivity of the monocyclic aromatic compound decreases.
또한, 상기 결정성 알루미노실리케이트계 촉매는 결정성 다공체로서 10 nm 이하의 중간기공을 포함하고 있으며, 미세기공 크기가 1 ~ 8 Å 범위인 것을 사용한다. 이때 결정성 다공체의 기공 크기가 상기 범위를 만족시키지 못하는 경우는 단환 방향족 화합물의 생산성이 저하되기 때문에 바람직하지 않다.In addition, the crystalline aluminosilicate-based catalyst is a crystalline porous body and includes an intermediate pore of 10 nm or less, and a micropore size of 1 to 8 mm 2 is used. At this time, if the pore size of the crystalline porous body does not satisfy the above range, it is not preferable because the productivity of the monocyclic aromatic compound decreases.
한편, 상기 결정성 알루미노실리케이트계 촉매는 단독으로 사용될 수도 있지만, 상기 결정성 알루미노실리케이트계 촉매는 필요에 따라 갈륨(Ga), 아연(Zn), 백금(Pt), 팔라듐(Pd), 텅스텐(W), 코발트(Co) 및 철(Fe)로 구성된 군에서 선택되는 1종 이상의 조촉매를 더 포함할 수도 있다. On the other hand, the crystalline aluminosilicate-based catalyst may be used alone, but the crystalline aluminosilicate-based catalyst may be gallium (Ga), zinc (Zn), platinum (Pt), palladium (Pd), tungsten as required. (W), cobalt (Co) and iron (Fe) may further include one or more cocatalysts selected from the group consisting of.
상기 조촉매로 포함되는 금속원소(A)의 함량은 결정성 알루미노실리케이트계 촉매 중의 알루미늄 원자(Al)를 기준으로 할 때 A/Al의 중량비가 0.01 ~ 2.5를 유지하는 것이 좋다. 바람직하기로는 알루미늄 원자를 기준으로 조촉매 금속원소(A)의 중량비(즉, A/Al의 중량비)가 0.1 ~ 1이 되도록 포함하는 것이다.When the content of the metal element (A) contained in the cocatalyst is based on the aluminum atom (Al) in the crystalline aluminosilicate-based catalyst, the weight ratio of A / Al is preferably maintained at 0.01 to 2.5. Preferably, the weight ratio of the cocatalyst metal element (A) based on the aluminum atom (that is, the weight ratio of A / Al) is included to be 0.1 to 1.
전술된 바와 같은 복합촉매(150)가 충진한 반응기(100) 내로 합성가스가 유입되면, 반응기 내에서 합성가스의 피셔-트롭쉬 반응으로 탄화수소가 형성되고, 상기 형성된 탄화수소는 탈수소화 반응으로 단환 방향족 화합물이 제조된다. 이때, 상기 반응기(100)로는 슬러리층 반응기, 고정층 반응기, 유동층 반응기 등의 통상의 피셔-트롭쉬 합성 공정에서 사용할 수 있는 반응기면 제한 없이 적용 가능할 수 있다.When the synthesis gas flows into the reactor 100 filled with the complex catalyst 150 as described above, hydrocarbons are formed by Fischer-Tropsch reaction of the synthesis gas in the reactor, and the formed hydrocarbons are monocyclic aromatic by dehydrogenation reaction. The compound is prepared. At this time, the reactor 100 may be applied without limitation to the reactor surface that can be used in a conventional Fischer-Tropsch synthesis process such as a slurry bed reactor, a fixed bed reactor, a fluidized bed reactor, and the like.
일반적으로 철계 촉매 기반 합성가스의 피셔-트롭쉬 반응에서 단쇄 탄화수소의 선택도를 높이고, 메탄(CH4)으로 선택도를 낮추기 위해서는 반응온도를 340 ℃ 이하로 낮게 유지하면서 반응 압력을 10 bar 이상 높게 유지하는 것이 바람직한 반면, 단쇄 탄화수소의 탈수소화 반응을 유도하여 단환 방향족 화합물의 선택도를 높이기 위해서는 반응온도를 400 ℃ 이상 높게 유지하면서 반응압력을 5 bar 이하로 낮게 유지하는 것이 바람직하므로, 두 반응을 원스텝 공정으로 하나의 반응기에서 진행할 경우, 각 반응 생성물의 수율을 최대화시키기 위한 단일화된 반응 조건을 찾기 어려운 문제점이 있다. In general, in order to increase the selectivity of short-chain hydrocarbons in the Fischer-Tropsch reaction of an iron-based catalyst-based synthesis gas and to lower the selectivity with methane (CH 4 ), the reaction pressure is maintained at a temperature lower than 340 ° C. and the reaction pressure is higher than 10 bar. On the other hand, in order to increase the selectivity of a monocyclic aromatic compound by inducing a dehydrogenation reaction of a short-chain hydrocarbon, it is preferable to keep the reaction temperature high at 400 ° C. or higher while maintaining a reaction pressure as low as 5 bar or less. When proceeding in one reactor in a one-step process, there is a problem in that it is difficult to find a single reaction condition for maximizing the yield of each reaction product.
이에, 본 발명에서는 원스텝 공정에서 단환 방향족 화합물의 수율을 극대화시키기 위해 촉매의 조성과, 반응 온도, 반응 압력 및 합성 가스의 조성비를 제어함으로써, 피셔-트롭쉬 합성반응과 탈수소화 방향족화 반응 각각의 최적 조건을 확보해야 하는 다단 공정 구축문제를 해결할 수 있다. Thus, in the present invention, by controlling the composition of the catalyst, the reaction temperature, the reaction pressure and the composition ratio of the synthesis gas to maximize the yield of the monocyclic aromatic compound in a one-step process, each of the Fischer-Tropsch synthesis reaction and the dehydrogenation aromatization reaction It is possible to solve the problem of building a multi-stage process that requires securing optimum conditions.
본 발명의 반응조건은 250 ℃ ~ 400 ℃의 온도범위에서 1 bar ~ 25 bar의 압력범위, 바람직하게는 340 ℃ ~ 380 ℃의 온도범위에서 10 bar ~ 20 bar의 압력범위로 진행할 수 있다.The reaction conditions of the present invention can proceed to a pressure range of 1 bar to 25 bar in a temperature range of 250 ° C to 400 ° C, preferably a pressure range of 10 bar to 20 bar in a temperature range of 340 ° C to 380 ° C.
상기한 반응에 있어서, 상기 반응 온도가 250 ℃ 미만일 경우, 탈수소화 방향족화 반응에 대한 활성이 나타나지 않아 단환 방향족 화합물의 수율이 낮아지는 문제점이 발생될 수 있고, 400 ℃를 초과할 경우에는 메탄화 반응이 우세하게 일어나 대부분의 생성물이 메탄(CH4)과 이산화탄소로 발생될 수 있으며, 촉매의 신터링(sintering)과 과도한 탄소 침적으로 인해 촉매의 수명이 짧아지는 문제점이 발생될 수 있다.In the above reaction, when the reaction temperature is less than 250 ° C, there may be a problem that the yield of the monocyclic aromatic compound is lowered because there is no activity for the dehydrogenation aromatization reaction, and when it exceeds 400 ° C, methanation Since the reaction is predominant, most of the products can be generated with methane (CH 4 ) and carbon dioxide, and a problem of shortening the life of the catalyst may occur due to sintering of the catalyst and excessive carbon deposition.
또한, 상기한 반응에 있어서, 상기 반응 압력이 25 bar를 초과할 경우에는 결정성 알루미노실리케이트계 촉매 내 물질전달의 문제로 과도한 탄화수소 탈수소화 반응이 일어나 다환 방향족 화합물이 주로 생성되거나 탄소침적의 문제가 발생될 수 있으며, 고압 유지를 위한 안정상의 문제로 공정 운전이 까다로운 문제점이 발생될 수 있다. In addition, in the above reaction, when the reaction pressure exceeds 25 bar, excessive hydrocarbon dehydrogenation reaction occurs due to the problem of mass transfer in the crystalline aluminosilicate-based catalyst, and polycyclic aromatic compounds are mainly produced or carbon deposition problems. May occur, and a problem that is difficult to operate the process may occur due to a stability problem for maintaining high pressure.
이와 같은 반응으로 제조된 생성물은 벤젠, 톨루엔, 에틸벤젠, 자일렌 등의 하나의 고리를 가지는 방향족 화합물인 단환 방향족 화합물과 경질 탄화수소(C1 ~ C4)가 반응 부산물로서 포함될 수 있다. 이에, 본 발명에서는 기/액상 분리장치 등을 통한 분리정제 단계를 후단에 추가하여 기상의 경질 탄화수소(C1 ~ C4)와 액상의 단환 방향족 화합물을 분리할 수 있다.The product produced by such a reaction may include a monocyclic aromatic compound, which is an aromatic compound having one ring, such as benzene, toluene, ethylbenzene, and xylene, and light hydrocarbons (C1 to C4) as reaction by-products. Thus, in the present invention, a separation / purification step through a gas / liquid separation device or the like can be added to the rear stage to separate gaseous light hydrocarbons (C1 to C4) and liquid monocyclic aromatic compounds.
상기 기/액상 분리장치의 증류온도는 -5 ℃ ~ 5 ℃가 바람직하다. 상기 분리장치의 온도가 -5 ℃ 미만이면 반응의 부생성물인 물이 동결되어 분리장치가 파손될 우려가 있기 때문에 바람직하지 않고, 5 ℃를 초과하면 경질 탄화수소(C1 ~ C4)와 액상 탄화수소(C5+)의 분리가 미흡하여 바람직하지 않다.The distillation temperature of the gas / liquid separation device is preferably -5 ° C to 5 ° C. If the temperature of the separator is less than -5 ° C, it is not preferable because water, a by-product of the reaction, may be frozen, and the separator may be damaged. If it exceeds 5 ° C, light hydrocarbons (C1 to C4) and liquid hydrocarbons (C5 +) Is not preferred because of insufficient separation.
또한, 상기 기/액상 분리장치를 통해 분리된 C1 ~ C4의 경질탄화수소는 합성가스 제조를 위한 개질 반응기로 재순환되어 사용될 수 있다.In addition, the light hydrocarbons of C1 to C4 separated through the gas / liquid separation device may be recycled to a reforming reactor for syngas production.
이상에서 설명한 바와 같은 본 발명의 합성방법은 하기의 실시예를 통해 보다 구체적으로 설명하겠는 바, 본 발명이 이에 한정되는 것은 아니다.The synthesis method of the present invention as described above will be described in more detail through the following examples, but the present invention is not limited thereto.
<< 실시예Example 1-1 내지 1-8> 1-1 to 1-8>
도 1의 1/2인치 스테인리스 고정층 반응기에 촉매를 장입하고, 합성가스를 3600 mlh- 1gcat-1의 유속으로 22시간 동안 공급하고, 표 1의 조건에서 반응을 수행하여 단환 방향족 화합물을 제조하였다. 단환 방향족 화합물을 포함하여 생성된 탄화수소는 On-line GC(TCD, FID) 및 GC/MS를 사용하여 분석하였다. 이때, 상기 촉매로는 100Fe-6Cu-16Al-4K의 조성비를 가지는 철계 촉매 0.3 g와 HZSM-5(Si/Al=15)의 결정성 알루미노실리케이트계 촉매 0.6 g가 혼합된 복합촉매를 사용하였고, 합성가스는 H2/CO 몰비가 2(5 % Ar)인 합성가스를 사용하였으며, 반응온도 및 반응압력 조건에 따른 제조된 생성물의 조성을 분석한 결과를 표 2에 나타내었다.Charging the catalyst to the 1/2 inch stainless steel fixed bed reactor of Figure 1, the synthesis gas mlh 3600 - supplied for 22 hours at a flow rate of 1 gcat -1, and a reaction was carried out under the conditions shown in Table 1 was prepared in the monocyclic aromatic compound . Hydrocarbons produced including monocyclic aromatic compounds were analyzed using On-line GC (TCD, FID) and GC / MS. At this time, as the catalyst, a composite catalyst in which 0.3 g of an iron-based catalyst having a composition ratio of 100Fe-6Cu-16Al-4K and 0.6 g of a crystalline aluminosilicate-based catalyst of HZSM-5 (Si / Al = 15) was mixed was used. , Synthesis gas was used as a synthesis gas having a H 2 / CO molar ratio of 2 (5% Ar), and the results of analyzing the composition of the prepared product according to the reaction temperature and reaction pressure conditions are shown in Table 2.
<< 비교예Comparative example 1-1 및 1-2> 1-1 and 1-2>
실시예 1-1과 동일한 방법으로 반응을 수행하되, 촉매로는 복합촉매 대신 100Fe-6Cu-16Al-4K의 조성비를 가지는 철계 촉매 0.3 g만을 장입하였고, 하기 표 1의 조건으로 반응을 수행하여 제조된 생성물의 조성을 분석한 결과를 하기 표 2에 나타내었다.The reaction was carried out in the same manner as in Example 1-1, but as a catalyst, 0.3 g of an iron-based catalyst having a composition ratio of 100Fe-6Cu-16Al-4K was charged instead of a composite catalyst, and the reaction was carried out under the conditions in Table 1 below. Table 2 shows the results of analyzing the composition of the product.
구분division 촉매catalyst 반응 조건Reaction conditions
온도(℃)Temperature (℃) 압력(bar)Pressure (bar)
실시예 1-1Example 1-1 100Fe-6Cu-16Al-4K + HZSM-51) 100Fe-6Cu-16Al-4K + HZSM-5 1) 300300 2020
실시예 1-2Example 1-2 100Fe-6Cu-16Al-4K + HZSM-51) 100Fe-6Cu-16Al-4K + HZSM-5 1) 320320 2020
실시예 1-3Example 1-3 100Fe-6Cu-16Al-4K + HZSM-51) 100Fe-6Cu-16Al-4K + HZSM-5 1) 340340 2020
실시예 1-4Example 1-4 100Fe-6Cu-16Al-4K + HZSM-51) 100Fe-6Cu-16Al-4K + HZSM-5 1) 360360 2020
실시예 1-5Example 1-5 100Fe-6Cu-16Al-4K + HZSM-51) 100Fe-6Cu-16Al-4K + HZSM-5 1) 380380 2020
실시예 1-6Example 1-6 100Fe-6Cu-16Al-4K + HZSM-51) 100Fe-6Cu-16Al-4K + HZSM-5 1) 340340 1One
실시예 1-7Example 1-7 100Fe-6Cu-16Al-4K + HZSM-51) 100Fe-6Cu-16Al-4K + HZSM-5 1) 340340 55
실시예 1-8Example 1-8 100Fe-6Cu-16Al-4K + HZSM-51) 100Fe-6Cu-16Al-4K + HZSM-5 1) 340340 1010
비교예 1-1Comparative Example 1-1 100Fe-6Cu-16Al-4K100Fe-6Cu-16Al-4K 320320 2020
비교예 1-2Comparative Example 1-2 100Fe-6Cu-16Al-4K100Fe-6Cu-16Al-4K 340340 2020
1) HZSM-5: Si/Al = 15, 비표면적 = 402.1 m2/g, 브뢴스테드산점/루이스산점 = 0.81, 기공 크기: 5.1~5.6Å1) HZSM-5: Si / Al = 15, specific surface area = 402.1 m 2 / g, Bronsted acid / Lewis acid = 0.81, pore size: 5.1-5.6 mm2
구분division CO 전환율(%)CO conversion rate (%) CO2 선택도(%)CO 2 selectivity (%) 생성물 분포(몰 %)Product distribution (mole%)
CH4 CH 4 C2 ~ C4C2 ~ C4 Olefin in C2 ~ C4Olefin in C2 ~ C4 C5+C5 + 단환 방향족 화합물(BTEX2))Monocyclic aromatic compound (BTEX 2) )
실시예 1-1Example 1-1 98.798.7 31.831.8 11.411.4 44.144.1 0.430.43 44.544.5 10.110.1
실시예 1-2Example 1-2 98.498.4 30.730.7 14.114.1 46.946.9 0.440.44 39.039.0 10.010.0
실시예 1-3Example 1-3 98.098.0 29.629.6 18.018.0 48.148.1 0.690.69 33.933.9 13.713.7
실시예 1-4Example 1-4 97.497.4 31.031.0 20.920.9 46.946.9 0.780.78 32.232.2 14.114.1
실시예 1-5Example 1-5 96.896.8 29.829.8 26.426.4 46.546.5 0.990.99 27.227.2 17.517.5
실시예 1-6Example 1-6 7.57.5 55.055.0 28.428.4 22.522.5 4848 49.149.1 7.97.9
실시예 1-7Example 1-7 96.696.6 35.535.5 26.926.9 43.043.0 2.02.0 30.130.1 16.916.9
실시예 1-8Example 1-8 97.697.6 32.132.1 21.421.4 46.746.7 0.950.95 31.931.9 18.318.3
비교예 1-1Comparative Example 1-1 98.398.3 29.829.8 10.510.5 31.931.9 74.374.3 57.657.6 --
비교예 1-2Comparative Example 1-2 98.098.0 31.031.0 12.912.9 31.331.3 76.676.6 55.855.8 --
2) BTEX: 벤젠(Benzene), 톨루엔(Toluene), 에틸벤젠(Ethylbenzene), 자일렌(Xylene)2) BTEX: Benzene, Toluene, Ethylbenzene, Xylene
표 2에 나타난 바와 같이, 비교예 1-1 및 1-2의 경우 대부분 단쇄 탄화수소가 생성되며, 올레핀의 선택도가 높고, 단환 방향족 화합물이 전혀 생성되지 않은 반면, 실시예 1-1 내지 1-9에서는 포화 탄화수소의 분포가 높고, 단환 방향족 화합물이 생성되는 것으로 나타났다. 또한, 실시예 1-1 내지 1-9에서는 반응온도 및 반응압력 조건에 의해 생성물 내의 단환 방향족 화합물의 선택도가 변화됨을 확인할 수 있었다. 즉, 반응 압력이 20 bar일 때 반응 온도가 380 ℃로 증가할수록 CO 전환율이 감소되고, 단환 방향족 화합물의 선택도가 증가되는 경향을 보였으며, 반응 온도가 340 ℃일 때 반응 압력이 증가함에 따라 CO 전환율이 증가되나, 1 bar의 낮은 압력 조건에서는 피셔-트롭쉬 합성반응의 활성이 낮아 원료인 합성가스가 거의 전환되지 않음을 확인할 수 있었다. 특히, 반응 조건이 340 ℃ ~ 380 ℃, 10 bar ~ 20 bar일 때 단환 방향족 화합물의 선택도가 가장 높은 수치를 보였다.As shown in Table 2, in the case of Comparative Examples 1-1 and 1-2, mostly short-chain hydrocarbons are generated, olefin selectivity is high, and monocyclic aromatic compounds are not produced at all, whereas Examples 1-1 to 1- In 9, the distribution of saturated hydrocarbons is high, and monocyclic aromatic compounds are produced. In addition, in Examples 1-1 to 1-9, it was confirmed that the selectivity of the monocyclic aromatic compound in the product was changed by reaction temperature and reaction pressure conditions. That is, when the reaction pressure is 20 bar, the CO conversion rate decreases as the reaction temperature increases to 380 ° C, and the selectivity of the monocyclic aromatic compound tends to increase. As the reaction temperature increases to 340 ° C, the reaction pressure increases. Although the CO conversion rate was increased, it was confirmed that at a low pressure of 1 bar, the activity of the Fischer-Tropsch synthesis reaction was low, so that the raw material synthesis gas was hardly converted. In particular, when the reaction conditions are 340 ℃ ~ 380 ℃, 10 bar ~ 20 bar showed the highest selectivity of the monocyclic aromatic compound.
<< 실시예Example 2-1 내지 2-3> 2-1 to 2-3>
상기 실시예 1-8과 동일 조건에서 원료로 사용된 합성가스의 H2/CO 몰비로 달리하여 합성반응을 진행하였고, 그 결과를 하기 표 3에 나타내었다.The synthesis reaction was carried out by varying the H 2 / CO molar ratio of the synthesis gas used as a raw material under the same conditions as in Example 1-8, and the results are shown in Table 3 below.
구분division 합성가스Syngas CO 전환율(%)CO conversion rate (%) CO2 선택도(%)CO 2 selectivity (%) 생성물 분포(몰 %)Product distribution (mole%)
H2/CO 몰비H 2 / CO molar ratio CH4 CH 4 C2 ~ C4C2 ~ C4 Olefin in C2 ~ C4Olefin in C2 ~ C4 C5+C5 + 단환 방향족 화합물(BTEX2))Monocyclic aromatic compound (BTEX 2) )
실시예 2-1Example 2-1 0.50.5 71.871.8 43.743.7 15.415.4 33.033.0 0.460.46 51.651.6 15.915.9
실시예 2-2Example 2-2 1One 97.197.1 44.544.5 17.017.0 43.443.4 0.690.69 39.639.6 20.020.0
실시예 2-3Example 2-3 22 97.697.6 32.132.1 21.421.4 46.746.7 0.950.95 31.931.9 18.318.3
2) BTEX: 벤젠(Benzene), 톨루엔(Toluene), 에틸벤젠(Ethylbenzene), 자일렌(Xylene)2) BTEX: Benzene, Toluene, Ethylbenzene, Xylene
표 3에 나타난 바와 같이, H2/CO의 몰비가 증가함에 따라 수성가스전환반응이 억제됨에 따라 CO2 선택도가 감소되고, 수소화(hydrogenation)가 촉진됨에 따라 단쇄 탄화수소의 선택도가 증가되는 반면, 단환 방향족 화합물의 선택도가 감소됨을 확인하였으며, H2/CO의 몰비가 0.5 이하인 경우, 코크스 발생으로 인한 압력이 증가되고, 촉매의 비활성화가 빠르게 나타났다. 특히, 합성 가스의 H2/CO 몰비가 1 ~ 2일 때 단환 방향족 화합물의 선택도가 가장 높은 수치를 보였다.As shown in Table 3, as the molar ratio of H 2 / CO increases, the selectivity of CO 2 decreases as the water gas conversion reaction is suppressed, and the selectivity of the short-chain hydrocarbon increases as hydrogenation is promoted. , It was confirmed that the selectivity of the monocyclic aromatic compound was reduced, and when the molar ratio of H 2 / CO was 0.5 or less, the pressure due to coke generation was increased, and the deactivation of the catalyst appeared quickly. In particular, when the H 2 / CO molar ratio of the synthesis gas was 1 to 2, the selectivity of the monocyclic aromatic compound showed the highest value.
<< 실시예Example 3-1 내지 3-8> 3-1 to 3-8>
상기 실시예 1-8과 동일 조건에서 촉매 조건을 하기 표 4의 조건으로 달리하여 합성반응을 진행하였고, 그 결과를 하기 표 5에 나타내었다.Under the same conditions as in Example 1-8, the catalytic conditions were changed to the conditions in Table 4 below, and the synthesis reaction was performed, and the results are shown in Table 5 below.
구분division 촉매catalyst
100Fe-6Cu-16Al-4K : HZSM-51) 중량비100Fe-6Cu-16Al-4K: HZSM-5 1) Weight ratio HZSM-51)의 Si/Al 몰비Si / Al molar ratio of HZSM-5 1)
실시예 3-1Example 3-1 1 : 41: 4 1515
실시예 3-2Example 3-2 1 : 31: 3 1515
실시예 3-3Example 3-3 1 : 21: 2 1515
실시예 3-4Example 3-4 1 : 11: 1 1515
실시예 3-5Example 3-5 1 : 0.51: 0.5 1515
실시예 3-6Example 3-6 1 : 21: 2 2525
실시예 3-7Example 3-7 1 : 21: 2 4040
실시예 3-8Example 3-8 1 : 21: 2 140140
1) HZSM-5: Si/Al = 15, 비표면적 = 402.1 m2/g, 브뢴스테드산점/루이스산점 = 0.811) HZSM-5: Si / Al = 15, specific surface area = 402.1 m 2 / g, Brønsted acid / Lewis acid = 0.81
구분division CO 전환율(%)CO conversion rate (%) CO2 선택도(%)CO 2 selectivity (%) 생성물 분포(몰 %)Product distribution (mole%)
CH4 CH 4 C2 ~ C4C2 ~ C4 Olefin in C2 ~ C4Olefin in C2 ~ C4 C5+C5 + 단환 방향족 화합물(BTEX2 ))Monocyclic aromatic compound (BTEX 2 ) )
실시예 3-1Example 3-1 97.697.6 33.033.0 21.121.1 49.049.0 0.990.99 29.729.7 20.220.2
실시예 3-2Example 3-2 97.897.8 30.930.9 23.523.5 47.847.8 0.990.99 28.728.7 18.718.7
실시예 3-3Example 3-3 97.697.6 32.132.1 21.421.4 46.746.7 0.950.95 31.931.9 18.318.3
실시예 3-4Example 3-4 97.597.5 34.834.8 18.218.2 42.742.7 1.601.60 39.139.1 1717
실시예 3-5Example 3-5 97.497.4 31.131.1 22.522.5 38.438.4 3.03.0 39.139.1 15.215.2
실시예 3-6Example 3-6 97.697.6 32.632.6 21.621.6 46.346.3 0.990.99 32.132.1 17.517.5
실시예 3-7Example 3-7 97.697.6 31.131.1 22.322.3 43.443.4 1.21.2 34.334.3 16.816.8
실시예 3-8Example 3-8 97.697.6 31.531.5 21.421.4 44.244.2 1.31.3 34.434.4 16.616.6
2) BTEX: 벤젠(Benzene), 톨루엔(Toluene), 에틸벤젠(Ethylbenzene), 자일렌(Xylene)2) BTEX: Benzene, Toluene, Ethylbenzene, Xylene
상기 표 5의 실시예 3-1 내지 3-5에 나타난 바와 같이, 결정성 알루미노실리케이트계 촉매의 혼합된 함량이 감소될수록 올레핀 함량과 C5 이상의 탄화수소 함량이 증가되는 반면, 단환 방향족 화합물의 선택도가 감소되는 것으로 나타났다.As shown in Examples 3-1 to 3-5 of Table 5, as the mixed content of the crystalline aluminosilicate-based catalyst decreases, the olefin content and the hydrocarbon content of C5 or higher increase, while the selectivity of the monocyclic aromatic compound Has been shown to decrease.
또한, 표 5의 실시예 3-5 내지 3-8에 나타난 바와 같이, 결정성 알루미노실리케이트계 촉매의 Si/Al 몰비가 증가함에 따라 C5 이상의 탄화수소와 올레핀의 선택도가 증가되는 반면, 단환 방향족 화합물의 선택도가 감소되는 것으로 나타났다. 특히, 철계 촉매와 결정성 알루미노실리케이트계 촉매의 중량비가 1 : 2 ~ 1 : 4이고, 결정성 알루미노실리케이트계 촉매의 Si/Al 몰비가 15 ~ 25일 때 단환 방향족 화합물의 선택도가 가장 높은 수치를 보였다. In addition, as shown in Examples 3-5 to 3-8 of Table 5, as the Si / Al molar ratio of the crystalline aluminosilicate-based catalyst increases, the selectivity of hydrocarbons and olefins of C5 or higher increases, while monocyclic aromatics It has been shown that the selectivity of the compound is reduced. In particular, when the weight ratio of the iron-based catalyst and the crystalline aluminosilicate-based catalyst is 1: 2 to 1: 4, and the Si / Al molar ratio of the crystalline aluminosilicate-based catalyst is 15 to 25, the selectivity of the monocyclic aromatic compound is the most. It showed a high figure.
본 발명은 상기한 실시예와 첨부한 도면을 참조하여 설명되었지만, 본 발명의 개념 및 범위 내에서 상이한 실시예를 구성할 수도 있다. 따라서 본 발명의 범위는 첨부된 청구범위 및 이와 균등한 것들에 의해 정해지며, 본 명세서에 기재된 특정 실시예에 의해 한정되지는 않는다.Although the present invention has been described with reference to the above-described embodiments and the accompanying drawings, different embodiments may be configured within the concept and scope of the present invention. Accordingly, the scope of the present invention is defined by the appended claims and equivalents thereof, and is not limited by the specific embodiments described herein.

Claims (10)

  1. 철계 촉매 및 결정성 알루미노실리케이트계 촉매가 혼합된 복합촉매 존재하에 합성가스를 반응시켜 단환 방향족 화합물을 제조하는 단계를 포함하는, 단환 방향족 화합물의 합성방법.A method of synthesizing a monocyclic aromatic compound comprising the step of preparing a monocyclic aromatic compound by reacting a synthesis gas in the presence of a mixed catalyst in which an iron-based catalyst and a crystalline aluminosilicate-based catalyst are mixed.
  2. 제1항에 있어서,According to claim 1,
    상기 반응은 250 ℃ ~ 400 ℃에서 1 bar ~ 25 bar로 수행하는 것을 특징으로 하는 단환 방향족 화합물의 합성방법.The reaction is a synthesis method of a monocyclic aromatic compound, characterized in that carried out at 1 bar ~ 25 bar at 250 ℃ ~ 400 ℃.
  3. 제1항에 있어서,According to claim 1,
    상기 반응은 340 ℃ ~ 380 ℃에서 5 bar ~ 20 bar로 수행하는 것을 특징으로 하는 단환 방향족 화합물의 합성방법.The reaction is a method of synthesizing a monocyclic aromatic compound, characterized in that carried out at 340 ℃ ~ 380 ℃ 5 bar ~ 20 bar.
  4. 제1항에 있어서,According to claim 1,
    상기 합성가스는 H2/CO의 몰비가 0.1 ~ 3 범위인 것을 특징으로 하는 단환 방향족 화합물의 합성방법. The synthesis gas is a method of synthesizing a monocyclic aromatic compound, characterized in that the molar ratio of H 2 / CO is in the range of 0.1 to 3.
  5. 제1항에 있어서, According to claim 1,
    상기 복합촉매는 철계 촉매 및 결정성 알루미노실리케이트계 촉매의 중량비가 1 : 0.1 내지 1 : 10인 것을 특징으로 하는 단환 방향족 화합물의 합성방법. The composite catalyst is a method for synthesizing a monocyclic aromatic compound, characterized in that the weight ratio of the iron-based catalyst and the crystalline aluminosilicate-based catalyst is 1: 0.1 to 1: 10.
  6. 제1항에 있어서, According to claim 1,
    상기 철계 촉매는 구리(Cu), 망간(Mn), 코발트(Co), 니켈(Ni), 아연(Zn), 알루미늄(Al), 나트륨(Na), 크롬(Cr), 실리콘(Si) 및 칼륨(K)으로 구성된 군에서 선택되는 1종 이상의 조촉매가 더 함유된 것을 특징으로 하는 단환 방향족 화합물의 합성방법.The iron catalyst is copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), sodium (Na), chromium (Cr), silicon (Si) and potassium A method for synthesizing a monocyclic aromatic compound further comprising at least one cocatalyst selected from the group consisting of (K).
  7. 제1항에 있어서,According to claim 1,
    상기 결정성 알루미노실리케이트계 촉매는 ZSM-5, H-beta, L-zeolite, Y-zeolite, SAPO-34, MCM-22 및 H-USY로 구성된 군에서 선택되는 1종 이상인 것을 특징으로 하는 단환 방향족 화합물의 합성방법.The crystalline aluminosilicate-based catalyst is monocyclic, characterized in that at least one member selected from the group consisting of ZSM-5, H-beta, L-zeolite, Y-zeolite, SAPO-34, MCM-22 and H-USY Method for synthesizing aromatic compounds.
  8. 제1항에 있어서,According to claim 1,
    상기 결정성 알루미노실리케이트계 촉매는 Si/Al의 몰비가 10 ~ 150인 것을 특징으로 하는 단환 방향족 화합물의 합성방법. The crystalline aluminosilicate-based catalyst is a synthesis method of a monocyclic aromatic compound, characterized in that the molar ratio of Si / Al is 10 ~ 150.
  9. 제1항에 있어서,According to claim 1,
    상기 결정성 알루미노실리케이트계 촉매는 갈륨(Ga), 아연(Zn), 백금(Pt), 팔라듐(Pd), 텅스텐(W), 코발트(Co) 및 철(Fe)로 구성된 군에서 선택되는 1종 이상의 조촉매가 더 함유된 것을 특징으로 하는 단환 방향족 화합물의 합성방법. The crystalline aluminosilicate-based catalyst is selected from the group consisting of gallium (Ga), zinc (Zn), platinum (Pt), palladium (Pd), tungsten (W), cobalt (Co) and iron (Fe) 1 Synthesis method of a monocyclic aromatic compound, characterized in that it contains more than one kind of co-catalyst.
  10. 제1항에 있어서,According to claim 1,
    상기 단환 방향족 화합물은 벤젠, 톨루엔, 에틸벤젠 및 자일렌으로 구성된 군에서 선택되는 1종 이상의 화합물을 포함하는 것을 특징으로 하는 단환 방향족 화합물의 합성방법. The monocyclic aromatic compound is a method for synthesizing a monocyclic aromatic compound comprising at least one compound selected from the group consisting of benzene, toluene, ethylbenzene and xylene.
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JPH0543484A (en) * 1991-08-16 1993-02-23 Res Assoc Util Of Light Oil Production of aromatic hydrocarbon
KR19990006692A (en) * 1997-06-06 1999-01-25 키아오 잉빈 Catalysts and methods for the conversion of aromatic hydrocarbons and their use in the production of aromatic hydrocarbons
JP2012062255A (en) * 2010-09-14 2012-03-29 Jx Nippon Oil & Energy Corp Method for manufacturing aromatic hydrocarbon
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