WO2014092474A1 - Catalyst for manufacturing synthetic gas through steam-carbon dioxide reforming, and method for manufacturing synthetic gas by using same - Google Patents

Catalyst for manufacturing synthetic gas through steam-carbon dioxide reforming, and method for manufacturing synthetic gas by using same Download PDF

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WO2014092474A1
WO2014092474A1 PCT/KR2013/011516 KR2013011516W WO2014092474A1 WO 2014092474 A1 WO2014092474 A1 WO 2014092474A1 KR 2013011516 W KR2013011516 W KR 2013011516W WO 2014092474 A1 WO2014092474 A1 WO 2014092474A1
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catalyst
reforming
steam
carbon dioxide
zirconia
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PCT/KR2013/011516
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French (fr)
Korean (ko)
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조원준
정종태
모용기
유혜진
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한국가스공사
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Priority to AU2013360529A priority Critical patent/AU2013360529B2/en
Priority to CN201380071801.0A priority patent/CN104955570B/en
Publication of WO2014092474A1 publication Critical patent/WO2014092474A1/en

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J37/04—Mixing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • Y02P20/141—Feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a catalyst for syngas production from natural gas using carbon dioxide, in particular a catalyst useful for syngas production by steam-carbon dioxide reforming (SCR) and a process for producing the same.
  • SCR steam-carbon dioxide reforming
  • the reforming process for producing a mixture of hydrogen and carbon monoxide, so-called syngas, from methane, which is the main component of natural gas, using a catalyst and an oxidant has been industrialized a long time ago and has become an important basic process of the chemical industry.
  • Synthetic gas produced by the methane reforming process is the basis of C1 chemistry and is applied to the process of producing methanol, hydrogen, ammonia, etc. Recently, the production of liquid fuels and oxygen-containing compounds through the synthesis gas production It is emerging as an important method of using natural gas.
  • Oxygen, water vapor, carbon dioxide, or a mixed gas thereof has been used as an oxidant for preparing synthesis gas from hydrocarbons, and many studies have been conducted to develop catalysts having different characteristics according to the type of oxidant.
  • Reforming methods for producing syngas from methane include steam reforming, carbon dioxide reforming, partial oxidation reforming, autothermal reforming, and triple reforming.
  • the steam reforming reaction proceeds according to the following Scheme 1, and mainly a nickel-based catalyst is used.
  • Some supported zirconia supported catalysts are known as steam reforming catalysts. That is, a zirconia-supported nickel catalyst in which cobalt is added to nickel has been disclosed as a steam reforming catalyst for hydrocarbons (US Pat. No. 4,026,823 (1975)). In another method, a titration of a metal such as lanthanum, cerium, and silver to a nickel catalyst A catalyst in which the ratio is added as a cocatalyst supported on common carriers such as alumina, silica, magnesia, zirconia and the like has been disclosed (US Pat. No. 4,060,498).
  • Korean Patent Registration No. 10-0394076 Ni-based reforming catalyst for syngas production and a method for producing syngas from natural gas by steam reforming using the same
  • the nickel-based reforming catalyst (Ni / Ce-Zr 2 ) for syngas production is characterized in that 5 to 20% by weight of nickel is supported on a zirconia carrier modified with cerium.
  • the catalyst was prepared by preparing a zirconia carrier or a zirconia carrier modified with cerium using a co-precipitation method or a sol-gel method and then supporting nickel by an impregnation method or a melting method.
  • DME dimethyl ether
  • an expensive noble metal catalyst has been proposed in which carbon deposition is not a problem.
  • US Pat. No. 5,068,057 discloses Pt / Al 2 O 3 and Pd / Al 2 O 3 catalysts
  • WO 92 / 11,199 discloses high noble metal supported alumina catalysts such as iridium, rhodium and ruthenium. It has been shown to exhibit activity and long lifespan.
  • the noble metal catalyst is unsuitable for industrial use because of its high resistance to carbon deposition and good activity compared to the nickel catalyst, while being expensive.
  • the present invention provides a nickel-based reforming catalyst for syngas production which can produce syngas or hydrogen with high yield while maintaining long life by preventing catalyst deactivation due to coke formation because of excellent activity and stability of the steam-carbon dioxide reforming reaction catalyst. I would like to.
  • the present invention provides a method for producing a synthesis gas by steam-carbon dioxide reforming reaction using the catalyst.
  • the catalyst according to the present invention is effective in minimizing carbon deposition and producing synthetic petrochemical products (wax, naphtha, diesel, etc.) in producing syngas by steam-carbon dioxide (SCR) reforming reaction of methane (2.0). Syngas having a ⁇ 0.2) can be produced, thereby reducing the production cost of the synthetic material.
  • Catalyst and process using the same according to the present invention can be applied to gas to liquid (GTL) FPSO (floating production, storage and offloading; floating production storage and unloading equipment), furthermore DME FPSO, so that various industrial applications are easy in the future. You can expect to lose.
  • GTL gas to liquid
  • FPSO floating production, storage and offloading; floating production storage and unloading equipment
  • 1 is a graph showing the conversion of methane generated from natural gas as a function of time during the synthesis gas manufacturing process according to an embodiment of the present invention.
  • FIG. 2 is a graph showing the molar ratio of hydrogen and carbon monoxide as a function of time in the constituents of the synthesis gas produced according to an embodiment of the present invention.
  • the present invention relates to a nickel-based reforming catalyst prepared using magnesium and lanthanide series which are relatively excellent in carbon deposition in a reforming catalyst by steam.
  • the weight ratio of nickel and magnesium oxide powder in step 2) is 1: 1 to 20, more preferably 1: 1 to 3.
  • the weight ratio of cerium, zirconia and alumina in step 1) is 1: 5 to 10: 20 to 40, it is not preferable because the carbon deposition occurs outside the above range.
  • the firing of step 3) can be carried out in air at a temperature of 700 ⁇ 1200 °C.
  • the mixing of step 3) may be carried out by dry mixing and then kneading and extruding. It is one of the distinguishing features from the prior art that the impregnation method or the melting method which is generally used for preparing a catalyst is not used.
  • the reforming catalyst is preferably supported by 5 to 20% by weight of nickel and magnesium as active ingredients in a cerium-modified zirconia / alumina support (Ce-ZrO 2 / Al 2 O 3 ). If the supported amount is out of the above range, it may be difficult to produce a synthesis gas in which the hydrogen / carbon monoxide ratio is close to two.
  • the present invention is also characterized in that the reforming reaction is carried out by supplying carbon dioxide, steam and methane under the conditions of the reaction temperature 700 ⁇ 1200 °C, reaction pressure 15 ⁇ 20 bar, space velocity 4000 ⁇ 7000 h -1 using the catalyst It provides a method for producing a synthesis gas. Since the ratio of hydrogen / carbon monoxide in the synthesis gas produced through the reforming reaction is 2.0 ⁇ 0.2, it is possible to easily provide an efficient synthesis gas for producing synthetic petrochemical products (wax, naphtha, diesel, etc.).
  • a nickel reforming catalyst is prepared by supporting a predetermined amount of nickel / magnesium metal on a zirconia / alumina carrier modified with cerium, thereby producing steam-carbon dioxide reforming reaction of methane natural gas using the same. Synthesis gas, which is a mixture of carbon monoxide and hydrogen, can be produced in high yield.
  • the nickel reforming catalyst used for the steam-carbon dioxide reforming reaction of methane natural gas according to the present invention contains 5 to 20 wt% of nickel and magnesium as active ingredients in a cerium-modified zirconia / alumina support (Ce-ZrO 2 / Al 2 O 3 ). It is preferable that it is a reforming catalyst supported by%. If the supported amount of nickel / magnesium is out of the above range and less than 5 wt% with respect to the cerium-modified zirconia / alumina carrier, there is a problem of low activity. If it exceeds 20 wt%, deactivation of the catalyst due to deposition of coke occurs. I can't.
  • the zirconia / alumina carrier (Ce-ZrO 2 / Al 2 O 3 ) modified cerium used as a carrier is a mixture of zirconia / alumina and cerium, the cerium (Ce) is 0.01 0.01 based on 1 mol of zirconia / alumina It is contained in a ⁇ 1.0 molar ratio range, there is a problem that the activity of the catalyst is lowered if cerium is modified in excess in excess of 1.0 molar ratio.
  • a method of modifying cerium on a zirconia-based / alumina carrier or a method of supporting nickel / magnesium is generally known, that is, a coprecipitation method, a precipitation deposition method, a sol-gel method. Dry mixing, kneading, extrusion and baking after dry mixing are used instead of the melting method and the impregnation method.
  • ceria, zirconia and alumina may be mixed in a desired ratio to obtain a zirconia / alumina carrier modified with cerium.
  • the mixing method is not particularly limited as long as it is a dry mixing method generally used in the industry such as a ball mill method.
  • nickel and magnesium a mixture of nickel oxide and magnesium oxide is mixed in powder form, mixed with a zirconia / alumina carrier modified with cerium, and kneaded and then baked. It is preferable to perform baking for 5 to 8 hours in air at the temperature of 700-1200 degreeC.
  • the catalyst when measuring the reforming activity of the catalyst, a typical fixed bed catalyst reactor manufactured in a laboratory is used.
  • the catalyst is molded and pulverized to have a particle size of 1 to 2 mm as a pretreatment process before the reaction, and then charged in a reactor by a required amount, and then reduced with 5% hydrogen at 700 ° C. for 1 hour before use.
  • methane and water vapor are injected into the reactor as a reactant in a molar ratio of 1: 1 to 3 and carbon dioxide of 0.4 to 1, and nitrogen is added as a diluent gas if necessary.
  • the temperature of the reactor is controlled in the range of 700 ⁇ 1200 °C by an electric heater and a programmable thermostat, the reaction pressure is 15 ⁇ 20 bar, the mass flow controller so that the space velocity is 4000 ⁇ 7000 h -1
  • Synthetic gas can be manufactured by continuously injecting a gas while controlling a flow rate of the gas with a mass flow controller.
  • the composition of the gas before and after the reaction is analyzed by gas chromatograph directly connected to the reactor, whereby a poropak column is used for separation of the gas.
  • the activity was measured at 750 ° C. over time, and the initial activity and the activity after 200 minutes were determined by the yield of hydrogen in the product and the conversion rate of methane. Measured through.
  • the method for producing syngas from natural gas using the reforming catalyst according to the present invention shows better activity than the activity of the conventional zirconia-supported nickel reforming catalyst, and also improves the activity of the catalyst to maintain high activity even at high gas space velocity. This suggests the possibility of using it as an industrial catalyst.
  • Ceria, zirconia, and alumina were put in the amounts shown in Table 1 below and mixed in a dried state.
  • Magnesium, nickel, alumina was also processed in the same process and mixed to the content of Table 2 below.
  • Each was calcined at the final 900 °C for 6 hours to prepare a powder. After mixing two kinds of powders (mixing) sufficiently, the temperature was raised to 750 ° C at a rate of 3 ° C / min and calcined for 6 hours. Physical properties of the catalyst obtained are shown in Table 1 and Table 2.
  • Table 1 Sample name Analysis item Content (wt%) 1 hole type CeO 2 1 to 3 MgO 1 to 3 NiO 3 ⁇ 8 ZrO 2 2 ⁇ 8 5 hole type CeO 2 1-5 MgO 1-5 NiO 3 ⁇ 8 ZrO 2 2 ⁇ 8
  • Example 1 The catalyst prepared in Example 1 was used in an SCR process (Steam, Carbon dioxide Reforming). Operating conditions were kept at the same temperature 900 °C, 18bar pressure was carried out reforming of methane at a space velocity of injection by altering the flow rate of the water vapor, carbon dioxide, methane 4000hr -1 and 7000hr -1. The ratio of the injected gas and the reaction result are shown in Table 3 below, FIGS. 1 and 2.
  • the catalyst of the example is much larger than that of the comparative example. This means that the reactor size can be minimized so that the same CH 4 conversion can be achieved with a capacity of 1/3 to 1/5 when designing a commercialized reactor, that is, it is economical.
  • the CO 2 content in the reaction gas can be increased by more than two times compared to the comparative example. Therefore, it is advantageous to use a gas having a high CO 2 content in the reaction gas, and also, there is an advantage that the CO 2 treatment capacity is higher than that of other processes because a large amount of CO 2 remaining after the reaction can be recovered.
  • the catalyst according to the present invention is effective in minimizing carbon deposition and producing synthetic petrochemical products (wax, naphtha, diesel, etc.) in producing syngas by steam-carbon dioxide (SCR) reforming reaction of methane (2.0). Syngas having a ⁇ 0.2) can be produced, thereby reducing the production cost of the synthetic material.
  • Catalyst and process using the same according to the present invention can be applied to gas to liquid (GTL) FPSO (floating production, storage and offloading; floating production storage and unloading equipment), furthermore DME FPSO, so that various industrial applications are easy in the future. You can expect to lose.
  • GTL gas to liquid
  • FPSO floating production, storage and offloading; floating production storage and unloading equipment

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Abstract

The present invention relates to a catalyst for manufacturing a synthetic gas from a natural gas by using carbon dioxide, and more specifically, to a catalyst useful for manufacturing a synthetic gas by means of steam-carbon dioxide reforming. The catalyst according to the present invention is manufactured by a method comprising the steps of: 1) manufacturing a zirconia and alumina support coated with cerium by using dry mixing; 2) preparing nickel and magnesium oxide powders; and 3) mixing and firing a powder of the support in step 1) and powders of metals in step 2). The ratio of hydrogen to carbon monoxide in the synthetic gas, which is manufactured by using the catalyst according to the present invention, can be controlled to 2.0±0.2, thereby easily providing the synthetic gas which is efficient for producing synthetic petrochemical products (such as wax, naphtha, and diesel).

Description

수증기-이산화탄소 개질에 의한 합성가스 제조용 촉매 및 이를 이용한 합성가스 제조방법Catalyst for syngas production by steam-carbon dioxide reforming and syngas production method using the same
본 발명은 이산화탄소를 이용한 천연가스로부터 합성가스 제조용 촉매, 특히 수증기-이산화탄소 개질(SCR)에 의한 합성가스 제조에 유용한 촉매 및 그 제조방법에 관한 것이다.The present invention relates to a catalyst for syngas production from natural gas using carbon dioxide, in particular a catalyst useful for syngas production by steam-carbon dioxide reforming (SCR) and a process for producing the same.
촉매와 산화제를 사용하여 천연가스의 주성분인 메탄으로부터 수소와 일산화탄소의 혼합물, 이른바 합성가스를 제조하는 개질공정은 이미 오래전에 공업화되어 화학산업의 중요한 기초공정이 되고 있다. The reforming process for producing a mixture of hydrogen and carbon monoxide, so-called syngas, from methane, which is the main component of natural gas, using a catalyst and an oxidant has been industrialized a long time ago and has become an important basic process of the chemical industry.
메탄의 개질공정에 의해 제조되는 합성가스는 C1 화학의 근간이 되는 물질로서 메탄올, 수소, 암모니아 등을 제조하는 공정에 적용되고 있으며, 최근 들어서는 합성가스 제조를 통한 액체 연료나 산소함유 화합물의 생산이 천연가스의 중요한 활용 방법으로 등장하고 있다.Synthetic gas produced by the methane reforming process is the basis of C1 chemistry and is applied to the process of producing methanol, hydrogen, ammonia, etc. Recently, the production of liquid fuels and oxygen-containing compounds through the synthesis gas production It is emerging as an important method of using natural gas.
탄화수소로부터 합성가스를 제조하기 위한 산화제로서 산소, 수증기, 이산화탄소 또는 이들의 혼합기체가 사용되어 왔고, 이러한 산화제의 종류에 따라 각각 다른 특성의 촉매를 개발하는 연구가 많이 진행되어 왔다.Oxygen, water vapor, carbon dioxide, or a mixed gas thereof has been used as an oxidant for preparing synthesis gas from hydrocarbons, and many studies have been conducted to develop catalysts having different characteristics according to the type of oxidant.
메탄으로부터 합성가스를 제조하는 개질 방법으로는 수증기 개질반응, 이산화탄소 개질반응, 부분산화 개질반응, 자열 개질반응, 삼중개질반응 등이 있다.Reforming methods for producing syngas from methane include steam reforming, carbon dioxide reforming, partial oxidation reforming, autothermal reforming, and triple reforming.
그 중에서 수증기 개질반응은 다음 반응식 1에 따라 진행되며, 주로 니켈계 촉매가 사용되고 있다.Among them, the steam reforming reaction proceeds according to the following Scheme 1, and mainly a nickel-based catalyst is used.
반응식 1 Scheme 1
CH4 + H2O → CO + 3H2, △H°298 = +206 kJ/molCH 4 + H 2 O → CO + 3H 2 , ΔH ° 298 = +206 kJ / mol
이러한 수증기 개질공정에서는 개질촉매의 탄소 침적에 의한 촉매 비활성화 방지가 가장 중요한 문제로 지적되고 있다. 상기 탄소 침적은 반응물 중의 수소원자 : 탄소원자의 몰비 및 산소원자 : 탄소원자의 몰비에 의해 열역학적으로 계산될 수 있기 때문에, 메탄의 수증기 개질공정에서는 탄소침적에 의한 촉매 비활성화를 막기 위해 수증기를 과량 첨가하여 수소원자 : 탄소원자의 몰비 및 산소원자 : 탄소원자의 몰비를 높여 사용하였다. 이에 따라, 수성가스화 반응이 상대적으로 촉진되어 수소 : 일산화탄소의 몰비가 3 : 1 이상인 합성가스가 얻어지는 바, 높은 수소함량을 필요로 하는 암모니아 제조 공정 또는 고농도의 수소 제조를 위한 합성가스 공정에 적합하다. 현재 공업적으로 사용되는 메탄의 수증기 개질공정은 730 ~ 860 ℃, 20 ~ 40 기압에서 메탄 : 수증기의 몰비가 1 : 4 ~ 6인 조건에서 운전되고 있다.In this steam reforming process, prevention of catalyst deactivation by carbon deposition of reforming catalyst is pointed out as the most important problem. Since the carbon deposition can be calculated thermodynamically by the molar ratio of hydrogen atoms: carbon atoms and oxygen atoms: carbon atoms in the reactants, the steam reforming process of methane adds an excess amount of steam to prevent catalyst deactivation by carbon deposition. The molar ratio of atom: carbon atom and oxygen atom: carbon atom was used to increase the molar ratio. Accordingly, the water gasification reaction is promoted relatively to obtain a syngas having a molar ratio of hydrogen: carbon monoxide 3: 1 or more, which is suitable for ammonia production processes requiring high hydrogen content or syngas processes for high concentration hydrogen production. . Currently, the steam reforming process of methane used industrially is operated at a molar ratio of 1: 4 to 6 at 730 to 860 ° C and 20 to 40 atmospheres.
한편, 수증기 개질반응에서 촉매로서 거의 대부분 니켈계 촉매가 사용되고 있다. 그러나 탄소침적에 의한 촉매 비활성화로 촉매수명이 단축된다는 문제가 있다 [S.H. Lee, W.C. Cho, W.S. Ju, B.H. Cho, Y.C. Lee, Y.S. Baek, Catal. Today 84 (2003) 133]. 기존의 수증기 개질 촉매보다 우수한 개질 촉매가 공업용 촉매로 개발되기 위해서는 코크 저항성뿐만 아니라 열안정성 및 기계적 안정성을 갖추어야 하는데, 이를 충족시키기 위해서는 수증기 개질 촉매의 α-알루미나 담체와 같이 적절한 담체의 선정이 매우 중요하다.On the other hand, almost all nickel-based catalysts are used as catalysts in the steam reforming reaction. However, there is a problem that catalyst life is shortened by catalyst deactivation by carbon deposition [S.H. Lee, W.C. Cho, W.S. Ju, B.H. Cho, Y.C. Lee, Y.S. Baek, Catal. Today 84 (2003) 133]. In order to develop an industrial catalyst that is superior to existing steam reforming catalysts, it is required to have not only coke resistance but also thermal stability and mechanical stability. To satisfy this, selection of a suitable carrier such as α-alumina carrier of the steam reforming catalyst is very important. Do.
상기 수증기 개질 촉매로서 지르코니아 담지 촉매가 일부 알려져 있다. 즉, 탄화수소의 수증기 개질 촉매로서 니켈에 코발트를 첨가한 지르코니아 담지 니켈 촉매가 공개된바 있고[미국특허 제4,026,823호(1975)], 또 다른 방법으로 니켈 촉매에 란타늄, 세륨 등의 금속과 은의 적정 비율을 조촉매로 첨가한 것을 일반적인 담체인 알루미나, 실리카, 마그네시아, 지르코니아 등에 담지한 촉매가 공개된 바 있다[미국특허 제4,060,498호]. 그리고, 지르코니아와 알루미나의 혼합 담체에 이리듐을 담지한 탄화수소의 수증기 개질 촉매가 각각 공개된바 있다[미국특허 제4,297,205호(1980), 제4,240,934호(1978)]. 그러나, 상기 방법들의 경우 높은 공간속도에서 수증기 개질반응에 적용할 경우 활성이 낮아지거나 촉매가 비활성화되는 문제가 있어 지르코니아를 수증기 개질 반응에 이용하기 위해서는 반응의 활성 및 고온에서의 열안정성, 그리고 높은 기체 공간속도에서의 활성을 유지할 수 있도록 수식할 필요가 있다. Some supported zirconia supported catalysts are known as steam reforming catalysts. That is, a zirconia-supported nickel catalyst in which cobalt is added to nickel has been disclosed as a steam reforming catalyst for hydrocarbons (US Pat. No. 4,026,823 (1975)). In another method, a titration of a metal such as lanthanum, cerium, and silver to a nickel catalyst A catalyst in which the ratio is added as a cocatalyst supported on common carriers such as alumina, silica, magnesia, zirconia and the like has been disclosed (US Pat. No. 4,060,498). In addition, steam reforming catalysts of hydrocarbons carrying iridium on a mixed carrier of zirconia and alumina have been disclosed (US Pat. Nos. 4,297,205 (1980) and 4,240,934 (1978)). However, in the case of the above methods, when applied to steam reforming reaction at high space velocity, there is a problem that activity is lowered or catalyst is inactivated. Therefore, in order to use zirconia in steam reforming reaction, the activity and thermal stability at high temperature and high gas It needs to be modified to maintain activity at space velocity.
이와 관련하여 한국특허등록 제10-0394076호(합성가스제조용 니켈계 개질촉매 및 이를 이용하는 수증기 개질에 의한 천연가스로부터 합성가스의 제조방법)는 지르코니아 1 몰을 기준으로 세륨이 0.01 ~ 1.0 몰비로 함유된 세륨으로 수식된 지르코니아 담체 상에 니켈 5 ~ 20중량%가 담지된 것을 특징으로 하는 합성가스 제조용 니켈계 개질촉매(Ni/Ce-Zr2)를 제시한다. 상기 촉매는 공침법 또는 졸겔법을 사용하여 지르코니아 담체 또는 세륨으로 수식된 지르코니아 담체를 제조한 후 함침법 또는 용융법에 의해 니켈을 담지함으로써 제조되었다. In this regard, Korean Patent Registration No. 10-0394076 (Ni-based reforming catalyst for syngas production and a method for producing syngas from natural gas by steam reforming using the same) contains cerium in a molar ratio of 0.01 to 1.0 mole based on 1 mole of zirconia The nickel-based reforming catalyst (Ni / Ce-Zr 2 ) for syngas production is characterized in that 5 to 20% by weight of nickel is supported on a zirconia carrier modified with cerium. The catalyst was prepared by preparing a zirconia carrier or a zirconia carrier modified with cerium using a co-precipitation method or a sol-gel method and then supporting nickel by an impregnation method or a melting method.
한편, 메탄의 이산화탄소 개질반응은 다음 반응식 2와 같이 진행되며, 메탄의 수증기 개질반응에서와 유사한 니켈계 촉매와 귀금속계 촉매가 주로 활용되고 있다. Meanwhile, the carbon dioxide reforming reaction of methane proceeds as shown in Scheme 2 below, and a nickel catalyst and a noble metal catalyst similar to those of steam reforming of methane are mainly used.
반응식 2 Scheme 2
CH4 + CO2 → 2CO + 2H2, △H°298 = +247.3 kJ/mol CH 4 + CO 2 → 2CO + 2H 2 , ΔH ° 298 = +247.3 kJ / mol
이산화탄소를 이용한 메탄의 개질반응은 일산화탄소 함량이 매우 높은 합성가스 (H2 : CO = 1 : 1)를 제조할 수 있기 때문에 생성된 합성가스는 디메틸에테르(dimethyl ether, DME)의 제조공정에 활용이 가능하다. 그러나, 탄소침적에 의한 촉매 비활성화가 심하게 일어나기 때문에 탄소침적이 크게 문제가 되지 않는 고가의 귀금속계 촉매가 제시되었다. 일례로, 미국특허 제5,068,057호에서는 Pt/Al2O3 및 Pd/Al2O3 촉매가 공지되었고, 국제특허공개 WO 92/11,199호에서는 이리듐을 비롯한 로듐, 루테늄 등의 귀금속 담지 알루미나 촉매가 높은 활성과 긴 수명을 나타낸다고 제시된 바 있다. 그러나 귀금속계 촉매는 니켈계 촉매에 비해 탄소침적에 대한 저항성이 크고 활성이 좋은 반면에 값이 비싸기 때문에 공업적으로 이용하기에는 부적합하다.The reforming reaction of methane using carbon dioxide can produce synthetic gas (H2: CO = 1: 1) with very high carbon monoxide content, so the synthesis gas can be used for the manufacturing process of dimethyl ether (DME). Do. However, since the catalyst deactivation by carbon deposition occurs badly, an expensive noble metal catalyst has been proposed in which carbon deposition is not a problem. For example, US Pat. No. 5,068,057 discloses Pt / Al 2 O 3 and Pd / Al 2 O 3 catalysts, and WO 92 / 11,199 discloses high noble metal supported alumina catalysts such as iridium, rhodium and ruthenium. It has been shown to exhibit activity and long lifespan. However, the noble metal catalyst is unsuitable for industrial use because of its high resistance to carbon deposition and good activity compared to the nickel catalyst, while being expensive.
이와 같이, 수증기와 이산화탄소를 이용한 메탄의 개질반응에서 탄소침적을 최소화하고, 공업적 활용이 용이하도록 생산 원가를 낮출 수 있는 촉매 개발이 꾸준히 시도되고 있다.As such, the development of a catalyst that minimizes carbon deposition in the reforming reaction of methane using water vapor and carbon dioxide and lowers the production cost to facilitate industrial utilization has been steadily attempted.
본 발명은 수증기-이산화탄소 개질 반응 촉매의 활성과 안정성이 뛰어나 코크 형성에 의한 촉매 비활성화를 방지하여 긴 수명을 유지하면서도 높은 수율로 합성가스 또는 수소를 제조할 수 있는 합성가스 제조용 니켈계 개질촉매를 제공하고자 한다.The present invention provides a nickel-based reforming catalyst for syngas production which can produce syngas or hydrogen with high yield while maintaining long life by preventing catalyst deactivation due to coke formation because of excellent activity and stability of the steam-carbon dioxide reforming reaction catalyst. I would like to.
상기 기술적 과제를 달성하기 위하여, 본 발명은 In order to achieve the above technical problem, the present invention
1) 건식혼합을 이용하여 세륨으로 수식된 지르코니아 및 알루미나 담체를 제조하는 단계;1) preparing a zirconia and alumina carrier modified with cerium using dry mixing;
2) 니켈 및 마그네슘 산화물 분말을 각각 준비하는 단계; 및 2) preparing nickel and magnesium oxide powders respectively; And
3) 단계 1)의 담체 분말과 단계 2)의 금속 분말을 혼합하여 소성하는 단계를 포함하는 방법에 의해 제조된, 합성가스를 제조하기 위한 개질반응용 촉매를 제공한다. 3) It provides a catalyst for the reforming reaction for producing a synthesis gas prepared by a method comprising the step of mixing the carrier powder of step 1) and the metal powder of step 2) and calcining.
또한 본 발명은 상기 촉매를 이용하여 수증기-이산화탄소 개질반응에 의해 합성가스를 제조하는 방법을 제공한다.In another aspect, the present invention provides a method for producing a synthesis gas by steam-carbon dioxide reforming reaction using the catalyst.
본 발명에 따른 촉매는 메탄의 수증기-이산화탄소(SCR) 개질반응에 의한 합성가스를 제조함에 있어 탄소침적을 최소화 하고 합성석유화학제품(왁스, 나프타, 디젤 등)을 생산하는데 효율적인 합성가스 비율(2.0±0.2)을 갖는 합성가스를 제조할 수 있고, 이로 인해 합성물질의 생산비용을 절감할 수 있다. 본 발명에 따른 촉매 및 이를 이용한 공정은 GTL(gas to liquid) FPSO(floating production, storage and offloading; 부유식 생산저장하역설비), 더 나아가 DME FPSO에 적용할 수 있어 앞으로 다양한 공업적 활용이 용이해 질 것을 기대할 수 있다.The catalyst according to the present invention is effective in minimizing carbon deposition and producing synthetic petrochemical products (wax, naphtha, diesel, etc.) in producing syngas by steam-carbon dioxide (SCR) reforming reaction of methane (2.0). Syngas having a ± 0.2) can be produced, thereby reducing the production cost of the synthetic material. Catalyst and process using the same according to the present invention can be applied to gas to liquid (GTL) FPSO (floating production, storage and offloading; floating production storage and unloading equipment), furthermore DME FPSO, so that various industrial applications are easy in the future. You can expect to lose.
도 1은 본 발명의 실시예에 따른 합성가스 제조과정 중 천연가스로부터 생성된 메탄의 전환율을 시간의 함수로 나타낸 그래프이다.1 is a graph showing the conversion of methane generated from natural gas as a function of time during the synthesis gas manufacturing process according to an embodiment of the present invention.
도 2는 본 발명의 실시예에 따라 제조된 합성가스의 구성성분 중 수소와 일산화탄소의 몰비를 시간의 함수로 나타낸 그래프이다.FIG. 2 is a graph showing the molar ratio of hydrogen and carbon monoxide as a function of time in the constituents of the synthesis gas produced according to an embodiment of the present invention.
본 발명은 수증기에 의한 개질촉매에서 탄소침적에 비교적 우수한 마그네슘 및 란탄계열을 이용하여 제조된 니켈계 개질 촉매에 관한 것이다. The present invention relates to a nickel-based reforming catalyst prepared using magnesium and lanthanide series which are relatively excellent in carbon deposition in a reforming catalyst by steam.
구체적으로 본 발명은 Specifically, the present invention
1) 건식혼합을 이용하여 세륨으로 수식된 지르코니아 및 알루미나 담체를 제조하는 단계;1) preparing a zirconia and alumina carrier modified with cerium using dry mixing;
2) 니켈 및 마그네슘 산화물 분말을 각각 준비하는 단계; 및 2) preparing nickel and magnesium oxide powders respectively; And
3) 단계 1)의 담체 분말과 단계 2)의 금속 분말을 혼합하여 소성하는 단계를 포함하는 방법에 의해 제조된, 합성가스를 제조하기 위한 개질반응용 촉매를 제공한다. 3) It provides a catalyst for the reforming reaction for producing a synthesis gas prepared by a method comprising the step of mixing the carrier powder of step 1) and the metal powder of step 2) and calcining.
본 발명의 바람직한 실시예에 의하면, 상기 단계 2)에서 니켈 및 마그네슘 산화물 분말의 중량비는 1: 1 ~ 20 이고, 더욱 바람직하게는 1: 1 ~ 3 이다.According to a preferred embodiment of the present invention, the weight ratio of nickel and magnesium oxide powder in step 2) is 1: 1 to 20, more preferably 1: 1 to 3.
본 발명의 바람직한 실시예에 의하면, 상기 단계 1)에서 세륨, 지르코니아 및 알루미나의 중량비는 1: 5 ~ 10 : 20 ~ 40 이고, 상기 범위를 벗어나면 탄소침적이 생겨 바람직하지 못하다.According to a preferred embodiment of the present invention, the weight ratio of cerium, zirconia and alumina in step 1) is 1: 5 to 10: 20 to 40, it is not preferable because the carbon deposition occurs outside the above range.
본 발명의 바람직한 실시예에 의하면, 상기 단계 3)의 소성은 700 ~ 1200 ℃ 의 온도에서 공기 중에서 실시할 수 있다. According to a preferred embodiment of the present invention, the firing of step 3) can be carried out in air at a temperature of 700 ~ 1200 ℃.
본 발명의 바람직한 실시예에 따르면, 상기 단계 3)의 혼합은 건식 혼합 후 건조하여 반죽 및 압출하는 과정에 의해 실시될 수 있다. 촉매 제조에 일반적으로 사용되는 함침법이나 용융법을 사용하지 않는 것이 종래기술과 구별되는 특징 중 하나이다. According to a preferred embodiment of the present invention, the mixing of step 3) may be carried out by dry mixing and then kneading and extruding. It is one of the distinguishing features from the prior art that the impregnation method or the melting method which is generally used for preparing a catalyst is not used.
상기 개질촉매는 세륨 수식된 지르코니아/알루미나 담체(Ce-ZrO2/Al2O3) 내에 활성성분인 니켈과 마그네슘이 5 ~ 20 중량% 로 담지된 것이 바람직하다. 담지량이 상기 범위를 벗어나면 수소/일산화탄소 비율이 2에 근접하는 합성가스를 제조하기 곤란할 수 있다. The reforming catalyst is preferably supported by 5 to 20% by weight of nickel and magnesium as active ingredients in a cerium-modified zirconia / alumina support (Ce-ZrO 2 / Al 2 O 3 ). If the supported amount is out of the above range, it may be difficult to produce a synthesis gas in which the hydrogen / carbon monoxide ratio is close to two.
본 발명은 또한 상기 촉매를 사용하여 반응온도 700 ~ 1200 ℃, 반응압력 15 ~ 20 bar, 공간속도 4000 ~ 7000 h-1의 조건으로 이산화탄소, 수증기 및 메탄을 공급하여 개질반응을 수행하는 것을 특징으로 하는 합성가스의 제조방법을 제공한다. 이러한 개질반응을 통하여 제조된 합성가스의 수소/일산화탄소의 비율이 2.0 ±0.2 이므로 합성석유화학제품(왁스, 나프타, 디젤 등)을 생산하는데 효율적인 합성가스를 용이하게 제공할 수 있다. The present invention is also characterized in that the reforming reaction is carried out by supplying carbon dioxide, steam and methane under the conditions of the reaction temperature 700 ~ 1200 ℃, reaction pressure 15 ~ 20 bar, space velocity 4000 ~ 7000 h -1 using the catalyst It provides a method for producing a synthesis gas. Since the ratio of hydrogen / carbon monoxide in the synthesis gas produced through the reforming reaction is 2.0 ± 0.2, it is possible to easily provide an efficient synthesis gas for producing synthetic petrochemical products (wax, naphtha, diesel, etc.).
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
기존의 수증기-이산화탄소 개질 반응에 사용된 촉매의 경우 높은 공간속도에서 촉매의 비활성화가 관측되거나 활성이 낮아지는 문제점을 나타내었다. 반면에, 본 발명에 사용된 니켈 개질촉매의 경우 세륨으로 수식된 지르코니아/알루미나 담체상에 니켈/마그네슘 금속을 일정량 담지시켜 니켈 개질 촉매를 제조함으로써, 이를 이용한 메탄 천연가스의 수증기-이산화탄소 개질반응시 일산화탄소 및 수소의 혼합물인 합성가스를 고수율로 제조할 수 있는 특징이 있다.In the case of the conventional catalysts used for steam-carbon dioxide reforming reactions, the catalyst deactivation is observed or the activity is deteriorated at high space velocity. On the other hand, in the case of the nickel reforming catalyst used in the present invention, a nickel reforming catalyst is prepared by supporting a predetermined amount of nickel / magnesium metal on a zirconia / alumina carrier modified with cerium, thereby producing steam-carbon dioxide reforming reaction of methane natural gas using the same. Synthesis gas, which is a mixture of carbon monoxide and hydrogen, can be produced in high yield.
본 발명에 따른 메탄 천연가스의 수증기-이산화탄소 개질반응에 사용하는 니켈 개질 촉매는 세륨 수식된 지르코니아/알루미나 담체(Ce-ZrO2/Al2O3)내에 활성성분인 니켈과 마그네슘이 5 ~ 20 중량% 로 담지된 개질촉매인 것이 바람직하다. 니켈/마그네슘의 담지량이 상기 범위를 벗어나 세륨 수식된 지르코니아/알루미나 담체에 대하여 5 중량% 미만이면 낮은 활성을 나타내는 문제가 있고, 20 중량%를 초과하면 코크의 침적에 의한 촉매의 비활성화가 발생하여 바람직하지 못하다. The nickel reforming catalyst used for the steam-carbon dioxide reforming reaction of methane natural gas according to the present invention contains 5 to 20 wt% of nickel and magnesium as active ingredients in a cerium-modified zirconia / alumina support (Ce-ZrO 2 / Al 2 O 3 ). It is preferable that it is a reforming catalyst supported by%. If the supported amount of nickel / magnesium is out of the above range and less than 5 wt% with respect to the cerium-modified zirconia / alumina carrier, there is a problem of low activity. If it exceeds 20 wt%, deactivation of the catalyst due to deposition of coke occurs. I can't.
이때, 담체로서 사용된 세륨이 수식된 지르코니아/알루미나 담체(Ce-ZrO2/Al2O3)는 지르코니아/알루미나와 세륨이 혼성되어 있는 것으로 지르코니아/알루미나 1 몰을 기준으로 세륨(Ce)이 0.01 ~ 1.0 몰비 범위로 함유되며, 세륨이 1.0 몰비를 초과하여 과량으로 수식되면 촉매의 활성이 낮아지는 문제가 있다. At this time, the zirconia / alumina carrier (Ce-ZrO 2 / Al 2 O 3 ) modified cerium used as a carrier is a mixture of zirconia / alumina and cerium, the cerium (Ce) is 0.01 0.01 based on 1 mol of zirconia / alumina It is contained in a ~ 1.0 molar ratio range, there is a problem that the activity of the catalyst is lowered if cerium is modified in excess in excess of 1.0 molar ratio.
본 발명에 따른 니켈계 개질촉매를 제조함에 있어서 지르코니아계/알루미나 담체에 세륨을 수식하는 방법이나 니켈/마그네슘을 담지하는 방법은 일반적으로 알려져 있는 공지의 방법, 즉 공침법, 침전퇴적법, 졸겔법, 용융법, 함침법 대신 건식 혼합 후 건조, 반죽, 압출, 소성하는 방법을 사용한다. In the preparation of the nickel-based reforming catalyst according to the present invention, a method of modifying cerium on a zirconia-based / alumina carrier or a method of supporting nickel / magnesium is generally known, that is, a coprecipitation method, a precipitation deposition method, a sol-gel method. Dry mixing, kneading, extrusion and baking after dry mixing are used instead of the melting method and the impregnation method.
가장 바람직하게는 원하는 비율로 세리아, 지르코니아, 알루미나를 혼합하여 세륨으로 수식된 지르코니아/알루미나 담체를 얻을 수 있다. 혼합방법은 볼밀 방법등 업계에서 일반적으로 사용되는 건식 혼합방법이면 특별히 제한되지 않는다. Most preferably, ceria, zirconia and alumina may be mixed in a desired ratio to obtain a zirconia / alumina carrier modified with cerium. The mixing method is not particularly limited as long as it is a dry mixing method generally used in the industry such as a ball mill method.
또한, 니켈과 마그네슘의 경우에도 산화니켈, 산화마그네슘의 산화물로 파우더 형태로 섞어 이를 세륨으로 수식된 지르코니아/알루미나 담체와 함께 혼합하여 반죽 및 압출 후 소성하는 과정을 거친다. 소성은 700 ~ 1200 ℃의 온도에서 공기중에서 5 ~ 8 시간 실시하는 것이 바람직하다.In addition, in the case of nickel and magnesium, a mixture of nickel oxide and magnesium oxide is mixed in powder form, mixed with a zirconia / alumina carrier modified with cerium, and kneaded and then baked. It is preferable to perform baking for 5 to 8 hours in air at the temperature of 700-1200 degreeC.
본 발명에서 촉매의 개질 활성을 측정시에는 실험실에서 제작한 전형적인 고정층 촉매 반응장치를 사용한다. 그리고, 반응전의 전처리 과정으로 상기 촉매를 1 ~ 2 mm 입자크기를 갖도록 성형, 분쇄한 후 필요한 양만큼 반응기에 충진한 후 반응하기 전에 5% 수소로 700 ℃에서 1시간 동안 환원한 후 사용한다.In the present invention, when measuring the reforming activity of the catalyst, a typical fixed bed catalyst reactor manufactured in a laboratory is used. In addition, the catalyst is molded and pulverized to have a particle size of 1 to 2 mm as a pretreatment process before the reaction, and then charged in a reactor by a required amount, and then reduced with 5% hydrogen at 700 ° C. for 1 hour before use.
그런 다음, 반응물로서 메탄과 수증기를 1 : 1 ~ 3의 몰비, 이산화탄소 0.4 ~ 1의 몰비로 반응기에 주입하고 필요한 경우에 질소를 희석기체로 첨가한다. 이때, 반응기의 온도는 전기히터와 프로그램 가능한 자동온도 조절장치에 의해 700 ~ 1200 ℃의 범위로 조절되며, 반응압력은 15 ~ 20 bar이고, 공간속도가 4000 ~ 7000 h-1가 되도록 질량 유량 조절기(Mass Flow Controller)로 기체의 유량을 조절하면서 기체를 주입하여 연속적으로 반응시킴으로써, 합성가스를 제조할 수 있다. 반응전후 기체의 조성은 반응장치에 직접 연결된 기체 크로마토그래프로 분석하며, 이때 기체의 분리를 위해서 프로팍(poropak) 컬럼이 사용된다.Then, methane and water vapor are injected into the reactor as a reactant in a molar ratio of 1: 1 to 3 and carbon dioxide of 0.4 to 1, and nitrogen is added as a diluent gas if necessary. At this time, the temperature of the reactor is controlled in the range of 700 ~ 1200 ℃ by an electric heater and a programmable thermostat, the reaction pressure is 15 ~ 20 bar, the mass flow controller so that the space velocity is 4000 ~ 7000 h -1 Synthetic gas can be manufactured by continuously injecting a gas while controlling a flow rate of the gas with a mass flow controller. The composition of the gas before and after the reaction is analyzed by gas chromatograph directly connected to the reactor, whereby a poropak column is used for separation of the gas.
이상과 같은 방법에서 개질촉매의 고온에서의 활성과 열안정성을 측정하기 위하여 750 ℃에서 활성을 시간의 흐름에 따라 측정하고, 초기 활성과 200분 후의 활성을 생성물 중의 수소의 수율 및 메탄의 전환율을 통하여 측정하였다. In the above method, in order to measure the activity and thermal stability of the reforming catalyst at high temperature, the activity was measured at 750 ° C. over time, and the initial activity and the activity after 200 minutes were determined by the yield of hydrogen in the product and the conversion rate of methane. Measured through.
본 발명에 따른 개질촉매를 이용하여 천연가스로부터 합성가스를 제조하는 방법은 기존 지르코니아 담지 니켈 개질 촉매의 활성보다 더 나은 활성을 나타내고, 또한 촉매의 활성 개선으로 높은 기체 공간속도에서도 높은 활성을 유지할 수 있어 공업용 촉매로 활용할 수 있는 가능성을 제시할 수 있다.The method for producing syngas from natural gas using the reforming catalyst according to the present invention shows better activity than the activity of the conventional zirconia-supported nickel reforming catalyst, and also improves the activity of the catalyst to maintain high activity even at high gas space velocity. This suggests the possibility of using it as an industrial catalyst.
이하, 본 발명을 다음의 실시예에 의거하여 더욱 상세히 설명하겠는바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited by the examples.
실시예 1Example 1
세리아, 지르코니아, 알루미나를 각각 하기 표 1의 함량이 되도록 넣고 건조된 상태에서 혼합하였다. 마그네슘, 니켈, 알루미나도 같은 공정으로 진행되며 하기 표 2의 함량이 되도록 혼합하였다. 각각 최종 900℃에서 6시간 동안 소성하여 파우더를 제조하였다. 두 종류의 파우더를 충분히 혼합(mixing)한 후 3℃/min의 속도로 750℃까지 승온하여 6시간 동안 소성시켰다. 얻어진 촉매의 물리적인 특성은 표1과 표2에 나타내었다.Ceria, zirconia, and alumina were put in the amounts shown in Table 1 below and mixed in a dried state. Magnesium, nickel, alumina was also processed in the same process and mixed to the content of Table 2 below. Each was calcined at the final 900 ℃ for 6 hours to prepare a powder. After mixing two kinds of powders (mixing) sufficiently, the temperature was raised to 750 ° C at a rate of 3 ° C / min and calcined for 6 hours. Physical properties of the catalyst obtained are shown in Table 1 and Table 2.
표 1
샘플명 분석항목 함량(wt%)
1 hole type CeO2 1~3
MgO 1~3
NiO 3~8
ZrO2 2~8
5 hole type CeO2 1~5
MgO 1~5
NiO 3~8
ZrO2 2~8
Table 1
Sample name Analysis item Content (wt%)
1 hole type CeO 2 1 to 3
MgO 1 to 3
NiO 3 ~ 8
ZrO 2 2 ~ 8
5 hole type CeO 2 1-5
MgO 1-5
NiO 3 ~ 8
ZrO 2 2 ~ 8
표 2
실시예 1 L축 강도 R축 강도 비표면적(m2/g) 벌크밀도(g/L)
3240.86 190.12 3.84 1.9
TABLE 2
Example 1 L-axis strength R-axis strength Specific surface area (m 2 / g) Bulk Density (g / L)
3240.86 190.12 3.84 1.9
실시예 2Example 2
실시예 1에서 제조한 촉매(1hole type)을 사용하여 SCR 공정(Steam, Carbon dioxide Reforming)에 적용하였다. 운전조건은 온도 900℃, 압력 18bar를 유지하였으며 수증기, 이산화탄소, 메탄의 주입 유량을 변경하여 4000hr-1 및 7000hr-1의 공간속도로 메탄의 개질반응을 수행하였다. 주입된 가스의 비율과 반응결과는 아래 표 3, 도 1 및 도 2와 같다. The catalyst prepared in Example 1 was used in an SCR process (Steam, Carbon dioxide Reforming). Operating conditions were kept at the same temperature 900 ℃, 18bar pressure was carried out reforming of methane at a space velocity of injection by altering the flow rate of the water vapor, carbon dioxide, methane 4000hr -1 and 7000hr -1. The ratio of the injected gas and the reaction result are shown in Table 3 below, FIGS. 1 and 2.
표 3
STM/CH4 CO2/CH4 4000hr-1 7000hr-1
H2/CO CH4 conv. H2/CO CH4 conv.
1.707 1.0 - - 2.22 98.98
1.195 1.0 - - 2.14 96.08
1.1 - - 2.03 95.88
1.024 1.0 2.27 91.77 2.00 94.84
1.1 2.17 91.81 - -
1.15 2.14 91.95 - -
1.2 2.11 92.02 - -
0.853 1.2 2.03 89.69 - -
TABLE 3
STM / CH 4 CO 2 / CH 4 4000hr -1 7000hr -1
H 2 / CO CH 4 conv. H 2 / CO CH 4 conv.
1.707 1.0 - - 2.22 98.98
1.195 1.0 - - 2.14 96.08
1.1 - - 2.03 95.88
1.024 1.0 2.27 91.77 2.00 94.84
1.1 2.17 91.81 - -
1.15 2.14 91.95 - -
1.2 2.11 92.02 - -
0.853 1.2 2.03 89.69 - -
상기 결과로부터, 개질반응을 통하여 제조된 합성가스의 수소/일산화탄소의 비율이 2.0±0.2인 것을 확인할 수 있고 메탄 전환율도 매우 높게 유지되고 있음을 알 수 있다. From the above results, it can be seen that the ratio of hydrogen / carbon monoxide of the synthesis gas produced through the reforming reaction is 2.0 ± 0.2, and the methane conversion is maintained very high.
비교예 1Comparative Example 1
함침법을 이용하고 활성성분으로서 Ni을 지지체인 Ce-Zr/MgAlOx 에 담지한 촉매(한국특허 출원 제2008-0075787호)를 사용하여 900℃, 압력 18bar의 반응 조건에서 혼합 개질반응을 수행한 결과는 표 4와 같다.Mixed reforming reaction was carried out at 900 ° C. under a pressure of 18 bar using a catalyst impregnated and supported on Ni-supported Ce-Zr / MgAlOx as an active ingredient (Korean Patent Application No. 2008-0075787). Is shown in Table 4.
표 4
반응몰비 (CH4/STM/CO2) 공간속도(hr-1) CH4 conv.
1/1.5/0.4 1300 95
1/1.5/0.39 1700 93
1/1.5/0.34 1700 97
Table 4
Molar ratio of reaction (CH 4 / STM / CO 2 ) Space velocity (hr -1 ) CH 4 conv.
1 / 1.5 / 0.4 1300 95
1 / 1.5 / 0.39 1700 93
1 / 1.5 / 0.34 1700 97
동등한 수준의 메탄 전환율을 나타내는 공간속도를 비교해 볼 때, 실시예의 촉매가 비교예의 경우보다 훨씬 큰 것을 알 수 있다. 이는 반응기 크기를 최소화할 수 있어서 상용화 반응기 설계시 1/3 ~ 1/5의 용량으로 같은 CH4 전환율을 나타낼 수 있다는 것, 즉 경제성이 높다는 것을 의미한다. Comparing the space velocities showing equivalent levels of methane conversion, it can be seen that the catalyst of the example is much larger than that of the comparative example. This means that the reactor size can be minimized so that the same CH 4 conversion can be achieved with a capacity of 1/3 to 1/5 when designing a commercialized reactor, that is, it is economical.
또한, 실시예의 촉매를 사용하는 경우 반응가스 중 CO2 함량을 비교예에 비해 2배 이상 높일 수 있음을 알 수 있다. 따라서, 반응가스 중 CO2 함량이 높은 가스를 사용할 수 있어 유리하고, 또한, 반응 후 남아있는 CO2를 다량 회수할 수 있어 타 공정보다 CO2 처리능력이 높다는 장점이 있다.In addition, when using the catalyst of the embodiment it can be seen that the CO 2 content in the reaction gas can be increased by more than two times compared to the comparative example. Therefore, it is advantageous to use a gas having a high CO 2 content in the reaction gas, and also, there is an advantage that the CO 2 treatment capacity is higher than that of other processes because a large amount of CO 2 remaining after the reaction can be recovered.
본 발명에 따른 촉매는 메탄의 수증기-이산화탄소(SCR) 개질반응에 의한 합성가스를 제조함에 있어 탄소침적을 최소화 하고 합성석유화학제품(왁스, 나프타, 디젤 등)을 생산하는데 효율적인 합성가스 비율(2.0±0.2)을 갖는 합성가스를 제조할 수 있고, 이로 인해 합성물질의 생산비용을 절감할 수 있다. 본 발명에 따른 촉매 및 이를 이용한 공정은 GTL(gas to liquid) FPSO(floating production, storage and offloading; 부유식 생산저장하역설비), 더 나아가 DME FPSO에 적용할 수 있어 앞으로 다양한 공업적 활용이 용이해 질 것을 기대할 수 있다.The catalyst according to the present invention is effective in minimizing carbon deposition and producing synthetic petrochemical products (wax, naphtha, diesel, etc.) in producing syngas by steam-carbon dioxide (SCR) reforming reaction of methane (2.0). Syngas having a ± 0.2) can be produced, thereby reducing the production cost of the synthetic material. Catalyst and process using the same according to the present invention can be applied to gas to liquid (GTL) FPSO (floating production, storage and offloading; floating production storage and unloading equipment), furthermore DME FPSO, so that various industrial applications are easy in the future. You can expect to lose.

Claims (9)

1) 건식혼합을 이용하여 세륨으로 수식된 지르코니아 및 알루미나 담체를 제조하는 단계;1) preparing a zirconia and alumina carrier modified with cerium using dry mixing;
2) 니켈 및 마그네슘 산화물 분말을 각각 준비하는 단계; 및 2) preparing nickel and magnesium oxide powders respectively; And
3) 단계 1)의 담체 분말과 단계 2)의 금속 분말을 혼합하여 소성하는 단계를 포함하는 방법에 의해 제조된, 합성가스를 제조하기 위한 개질반응용 촉매.3) A catalyst for reforming reaction for producing a synthesis gas, which is prepared by a process comprising the step of mixing the carrier powder of step 1) and the metal powder of step 2).
제1항에 있어서,The method of claim 1,
상기 개질반응은 수증기-이산화탄소 개질반응인 것을 특징으로 하는 개질반응용 촉매.The reforming reaction is a reforming catalyst, characterized in that the steam-carbon dioxide reforming reaction.
제1항에 있어서,The method of claim 1,
상기 단계 2)에서 니켈 및 마그네슘 산화물 분말의 중량비는 1: 2 ~ 10인 것을 특징으로 하는 개질반응용 촉매.The catalyst for the reforming reaction, characterized in that the weight ratio of nickel and magnesium oxide powder in step 2) is 1: 2 to 10.
제1항에 있어서,The method of claim 1,
상기 단계 1)에서 세륨, 지르코니아 및 알루미나의 중량비는 1: 5 ~ 10 : 20 ~ 40 인 것을 특징으로 하는 개질반응용 촉매.The weight ratio of cerium, zirconia and alumina in step 1) is 1: 5 ~ 10: 20 ~ 40 catalyst for the reforming reaction, characterized in that.
제1항에 있어서,The method of claim 1,
상기 단계 3)의 소성은 700 ~ 1200℃의 온도에서 공기 중에서 실시하는 것을 특징으로 하는 개질반응용 촉매.The calcination of step 3) is a reforming catalyst, characterized in that carried out in air at a temperature of 700 ~ 1200 ℃.
제1항에 있어서,The method of claim 1,
상기 단계 3)의 혼합은 건식 혼합 후 건조하여 반죽 및 압출하는 과정을 포함하는 것을 특징으로 하는 개질반응용 촉매.Mixing of step 3) is a catalyst for reforming, characterized in that it comprises a step of drying and kneading and extruding after dry mixing.
제1항에 있어서,The method of claim 1,
상기 개질촉매는 세륨 수식된 지르코니아/알루미나 담체(Ce-ZrO2/Al2O3) 내에 활성성분인 니켈과 마그네슘이 5 ~ 20 중량% 로 담지된 것을 특징으로 하는 개질촉매.The reforming catalyst is a reforming catalyst, characterized in that 5 to 20 wt% of nickel and magnesium as active ingredients are supported in a cerium-modified zirconia / alumina support (Ce-ZrO 2 / Al 2 O 3 ).
제1항 내지 제7항 중 어느 한 항의 촉매를 사용하여 반응온도 700 ~ 1200℃, 반응압력 15 ~ 20 bar, 공간속도 4000~7000 h-1의 조건으로 이산화탄소, 수증기 및 메탄을 공급하여 개질반응을 수행하는 것을 특징으로 하는 합성가스의 제조방법.Reforming by supplying carbon dioxide, steam and methane under the conditions of the reaction temperature 700 ~ 1200 ℃, reaction pressure 15 ~ 20 bar, space velocity 4000 ~ 7000 h -1 using the catalyst of any one of claims 1 to 7 Method of producing a synthesis gas, characterized in that to carry out.
제8항에 있어서,The method of claim 8,
상기 개질반응을 통하여 제조된 합성가스의 수소/일산화탄소의 비율이 2.0±0.2인 것을 특징으로 하는 방법.The ratio of hydrogen / carbon monoxide of the synthesis gas produced through the reforming reaction is characterized in that 2.0 ± 0.2.
PCT/KR2013/011516 2012-12-12 2013-12-12 Catalyst for manufacturing synthetic gas through steam-carbon dioxide reforming, and method for manufacturing synthetic gas by using same WO2014092474A1 (en)

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