WO2020091415A1 - Procédé de synthèse directe d'un composé aromatique monocyclique à partir d'un gaz de synthèse - Google Patents

Procédé de synthèse directe d'un composé aromatique monocyclique à partir d'un gaz de synthèse 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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Korean (ko)
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곽근재
박경아
강석창
전기원
이윤조
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한국화학연구원
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    • 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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    • B01J29/40—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
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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
    • B01J29/46—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
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    • 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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    • 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

La présente invention concerne un procédé de synthèse directe d'un composé aromatique monocyclique à partir de gaz de synthèse et, plus spécifiquement, un procédé de synthèse directe d'un composé aromatique monocyclique à partir de gaz de synthèse, le procédé permettant de simplifier un processus en un processus en une étape d'une condition de réaction spécifique lors de la préparation d'un composé aromatique monocyclique, permettant la production en masse d'un composé aromatique monocyclique en ayant à la fois une opération simple et une courte durée de traitement, et permettre la production directe d'un composé aromatique monocyclique avec un rendement élevé en utilisant un gaz de synthèse en tant que matériau, ce qui permet de résoudre un problème d'alimentation d'un composé aromatique monocyclique à valeur ajoutée élevée.
PCT/KR2019/014465 2018-10-30 2019-10-30 Procédé de synthèse directe d'un composé aromatique monocyclique à partir d'un gaz de synthèse WO2020091415A1 (fr)

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JP2012062255A (ja) * 2010-09-14 2012-03-29 Jx Nippon Oil & Energy Corp 芳香族炭化水素の製造方法
JP2012201802A (ja) * 2011-03-25 2012-10-22 Jx Nippon Oil & Energy Corp 単環芳香族炭化水素の製造方法
KR101600430B1 (ko) * 2015-01-08 2016-03-07 한국화학연구원 이산화탄소가 풍부한 합성가스로부터 단환 방향족 화합물 및 장쇄올레핀 화합물의 직접 합성방법

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JP2012139640A (ja) 2010-12-28 2012-07-26 Jx Nippon Oil & Energy Corp 単環芳香族炭化水素製造用触媒および単環芳香族炭化水素の製造方法
KR101418911B1 (ko) 2014-04-17 2014-07-14 한국에너지기술연구원 피셔-트롭쉬 합성반응을 이용한 탄화수소 화합물 및 그 제조방법

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JPH0543484A (ja) * 1991-08-16 1993-02-23 Res Assoc Util Of Light Oil 芳香族炭化水素の製造方法
KR19990006692A (ko) * 1997-06-06 1999-01-25 키아오 잉빈 방향족 탄화수소의 전환용 촉매 및 방법, 및 방향족 탄화수소의 제조에 있어서 그의 용도
JP2012062255A (ja) * 2010-09-14 2012-03-29 Jx Nippon Oil & Energy Corp 芳香族炭化水素の製造方法
JP2012201802A (ja) * 2011-03-25 2012-10-22 Jx Nippon Oil & Energy Corp 単環芳香族炭化水素の製造方法
KR101600430B1 (ko) * 2015-01-08 2016-03-07 한국화학연구원 이산화탄소가 풍부한 합성가스로부터 단환 방향족 화합물 및 장쇄올레핀 화합물의 직접 합성방법

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