KR101401170B1 - Lanthanum containing catalysts for preparing syn-gas by steam-carbon dioxide reforming reaction and process for preparing syn-gas using same - Google Patents
Lanthanum containing catalysts for preparing syn-gas by steam-carbon dioxide reforming reaction and process for preparing syn-gas using same Download PDFInfo
- Publication number
- KR101401170B1 KR101401170B1 KR1020120144030A KR20120144030A KR101401170B1 KR 101401170 B1 KR101401170 B1 KR 101401170B1 KR 1020120144030 A KR1020120144030 A KR 1020120144030A KR 20120144030 A KR20120144030 A KR 20120144030A KR 101401170 B1 KR101401170 B1 KR 101401170B1
- Authority
- KR
- South Korea
- Prior art keywords
- catalyst
- lanthanum
- reforming reaction
- gas
- carbon dioxide
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using 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
- C01B2203/02—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
-
- 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
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
Description
본 발명은 이산화탄소를 이용한 천연가스로부터 합성가스 제조용 촉매, 특히 수증기-이산화탄소 개질(SCR)에 의한 합성가스 제조에 유용한 란탄 함유 촉매 및 그 제조방법에 관한 것이다. The present invention relates to a catalyst for the production of syngas from natural gas using carbon dioxide, in particular a lanthanum-containing catalyst useful for the synthesis of synthesis gas by steam-carbon dioxide reforming (SCR), and a process for its preparation.
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 from methane, which is a main component of natural gas, using a catalyst and an oxidizing agent, so-called synthesis gas, has long been industrialized and becomes an important basic process in 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.Syngas produced by the methane reforming process is applied to the process of producing methanol, hydrogen, ammonia, etc. as the base material of the C1 chemistry. Recently, production of a liquid fuel or an oxygen- It is emerging as an important use of 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, steam, carbon dioxide, or a mixed gas thereof has been used as an oxidizing agent for producing a synthesis gas from hydrocarbons, and studies have been made to develop catalysts having different characteristics depending on the type of the oxidizing agent.
메탄으로부터 합성가스를 제조하는 개질 방법으로는 수증기 개질반응, 이산화탄소 개질반응, 부분산화 개질반응, 자열 개질반응, 삼중개질반응 등이 있다.Modification methods for producing synthesis gas 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
반응식 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 얻어지는바, 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 the reforming catalyst is pointed out as the most important problem. Since the carbon deposition can be thermodynamically calculated by the molar ratio of hydrogen atoms to carbon atoms in the reactants and the molar ratio of oxygen atoms to carbon atoms, in order to prevent catalyst deactivation due to carbon deposition in the steam reforming process of methane, Atom: carbon atom ratio and oxygen atom: carbon atom ratio were increased and used. As a result, the aqueous gasification reaction is relatively accelerated and a synthesis gas having a hydrogen / carbon monoxide molar ratio of 3: 1 or more is obtained, which is suitable for the ammonia production process requiring a high hydrogen content or the synthesis gas process for producing a high concentration of hydrogen . At present, the steam reforming process of methane used industrially is operated at a temperature of 730 ~ 860 ° C and a pressure of 20 ~ 40 atm, where the molar ratio of methane: water vapor is 1: 4 ~ 6.
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, nickel catalysts are mostly used as catalysts in the steam reforming reaction. However, there is a problem that the catalyst lifetime is shortened by catalyst deactivation due to carbon deposition [S. 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 a reforming catalyst superior to that of conventional steam reforming catalysts, it is necessary to have not only coke resistance but also thermal stability and mechanical stability. In order to satisfy this requirement, selection of an appropriate carrier such as an α-alumina carrier of 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. As the steam reforming catalyst, a zirconia supported catalyst is partially known. That is, a zirconia-supported nickel catalyst in which cobalt is added to nickel as a steam reforming catalyst for hydrocarbons has been disclosed (U.S. Patent No. 4,026,823 (1975)) as a steam reforming catalyst for hydrocarbons; another method is a method in which a titration of a metal such as lanthanum, A catalyst supported on alumina, silica, magnesia, zirconia or the like as a general carrier has been disclosed in U.S. Patent No. 4,060,498. A steam reforming catalyst for hydrocarbons carrying iridium is disclosed in a mixed carrier of zirconia and alumina (U.S. Patent No. 4,297,205 (1980), U.S. 4,240,934 (1978)). However, in the case of applying the above methods to steam reforming reaction at a high space velocity, there is a problem that the activity becomes low or the catalyst becomes inactive. In order to use zirconia for steam reforming reaction, It needs to be modified so as to maintain the activity at the 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. Korean Patent Registration No. 10-0394076 (a nickel-based reforming catalyst for synthesis gas production and a method for producing a syngas from natural gas by steam reforming using the same) comprises 0.01 to 1.0 molar percent of cerium based on 1 mol of zirconia, (Ni / Ce-Zr 2 ) for synthesis gas production, characterized in that 5 to 20% by weight of nickel is supported on a cerium-modified zirconia carrier. The catalyst is prepared by preparing a zirconia carrier or cerium-modified zirconia carrier using a coprecipitation method or a sol-gel method, and then carrying 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. On the other hand, the carbon dioxide reforming reaction of methane proceeds as shown in the following reaction formula 2, and nickel-based catalysts and noble metal-based catalysts similar to those in the steam reforming reaction of methane are mainly utilized.
반응식 2Scheme 2
CH4 + CO2 → 2CO + 2H2, △H°298 = +247.3 kJ/mol CH 4 + CO 2 ? 2CO + 2H 2 ,? H ° 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.Since the reforming reaction of methane using carbon dioxide can produce a synthesis gas (H 2 : CO = 1: 1) having a very high carbon monoxide content, the synthesis gas is utilized in the production process of dimethyl ether (DME) It is possible. However, since the deactivation of the catalyst by carbon deposition is severe, expensive noble metal-based catalysts are proposed, in which carbon deposition is not a serious problem. For example, U.S. Patent No. 5,068,057 discloses Pt / Al 2 O 3 and Pd / Al 2 O 3 catalysts, and International Patent Publication No. WO 92 / 11,199 discloses that noble metal-supported alumina catalysts such as rhodium and ruthenium, Activity and long life. However, the noble metal-based catalysts are more resistant to carbon deposition than the nickel-based catalysts, and have high activity, but are not suitable for industrial use because they are expensive.
이와 같이, 수증기와 이산화탄소를 이용한 메탄의 개질반응에서 탄소침적을 최소화하고, 공업적 활용이 용이하도록 생산 원가를 낮출 수 있는 촉매 개발이 꾸준히 시도되고 있다.
In this way, development of a catalyst capable of minimizing carbon deposition and lowering the production cost so as to facilitate industrial utilization in the reforming reaction of methane using steam and carbon dioxide has been continuously tried.
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 synthesis gas production capable of producing syngas or hydrogen at a high yield while maintaining long lifetime by preventing the inactivation of the catalyst due to the formation of coke due to excellent activity and stability of the steam-carbon dioxide reforming catalyst I want to.
상기 기술적 과제를 달성하기 위하여, 본 발명은 According to an aspect of the present invention,
1) 습식혼합 또는 건식볼밀 방식으로 란탄 및 세륨으로 수식된 지르코니아 및 알루미나 담체를 제조하는 단계;1) preparing zirconia and alumina carriers modified with lanthanum and cerium in a wet mixing or dry ball milling manner;
2) 단계 1)의 담체 분말과 니켈 분말을 혼합하여 소성하는 단계를 포함하는 방법에 의해 제조된, 합성가스를 제조하기 위한 개질반응용 촉매를 제공한다. 2) mixing the carrier powder and the nickel powder of step 1) and firing the mixture, and then calcining the mixture.
또한 본 발명은 상기 촉매를 이용하여 수증기-이산화탄소 개질반응에 의해 합성가스를 제조하는 방법을 제공한다.
The present invention also provides a method for producing a syngas by a steam-carbon dioxide reforming reaction using the catalyst.
본 발명에 따른 촉매는 메탄의 수증기-이산화탄소 개질반응(SCR)에 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 용이해질 것을 기대할 수 있다. The catalyst according to the present invention has a syngas ratio (2.0) which is effective in minimizing carbon deposition and producing synthetic petrochemical products (wax, naphtha, diesel, etc.) in the production of syngas by the steam-carbon dioxide reforming reaction (SCR) Lt; RTI ID = 0.0 > + -0.2), < / RTI > The catalyst according to the present invention and the process using the same can be applied to GTL (gas to liquid) FPSO (floating production, storage and offloading), and further DME FPSO, Can be expected.
도 1은 본 발명의 실시예 1 및 6 조건에 따라 제조된 합성가스의 구성성분 중 수소와 일산화탄소의 몰비를 나타낸 그래프이다.
도 2는 본 발명의 실시예 1 및 6 조건에 따른 합성가스 제조과정 중 천연가스로부터 생성된 메탄의 전환율을 나타낸 그래프이다.1 is a graph showing molar ratios of hydrogen and carbon monoxide among constituents of synthesis gas produced according to the conditions of Examples 1 and 6 of the present invention.
2 is a graph showing the conversion of methane produced from natural gas during synthesis gas production according to the conditions of Examples 1 and 6 of the present invention.
본 발명은 수증기에 의한 개질촉매에서 탄소침적에 비교적 우수한 니켈 및 란탄계열을 이용하여 제조된 니켈계 개질 촉매에 관한 것이다. The present invention relates to nickel-based reforming catalysts prepared using nickel and lanthanum series which are relatively good for carbon deposition in steam reforming catalysts.
구체적으로 본 발명은 Specifically,
1) 습식 또는 건식볼밀 방식으로 란탄 및 세륨으로 수식된 지르코니아 및 알루미나 담체를 제조하는 단계;1) preparing a zirconia and alumina carrier modified with lanthanum and cerium in a wet or dry ball mill manner;
2) 단계 1)의 담체 분말과 니켈 분말을 혼합하여 소성하는 단계를 포함하는 방법에 의해 제조된, 합성가스를 제조하기 위한 개질반응용 촉매를 제공한다. 2) mixing the carrier powder and the nickel powder of step 1) and firing the mixture, and then calcining the mixture.
본 발명의 바람직한 실시예에 의하면, 상기 개질촉매(NiO-La/Ce-ZrO2/Al2O3)는 란탄 및 세륨 수식된 지르코니아/알루미나 담체 내에 란탄 1 ~ 7 중량% 함유될 수 있다.According to a preferred embodiment of the present invention, the reforming catalyst (NiO-La / Ce-ZrO 2 / Al 2 O 3 ) may contain 1 to 7% by weight of lanthanum in a lanthanum and cerium-modified zirconia / alumina carrier.
본 발명의 바람직한 실시예에 의하면, 상기 단계 2)의 소성은 700 ~ 1200℃의 온도에서 공기 중에서 실시할 수 있다. According to a preferred embodiment of the present invention, the firing of the step 2) may be carried out in air at a temperature of 700 to 1200 ° C.
본 발명의 바람직한 실시예에 따르면, 상기 단계 2)의 혼합은 건식 볼밀 또는 습식혼합한 후 건조하여 반죽 및 압출하는 과정에 의해 실시될 수 있다. According to a preferred embodiment of the present invention, the mixing of step 2) may be carried out by dry ball milling or wet mixing followed by drying and kneading and extruding.
본 발명의 바람직한 실시예에 의하면, 상기 개질촉매(NiO-La/Ce-ZrO2/Al2O3)는 란탄 및 세륨 수식된 지르코니아/알루미나 담체 내에 니켈이 5 ~ 20 중량% 로 담지된다. 담지량이 상기 범위를 벗어나면 일산화탄소 1몰에 대한 수소의 몰비가 2에 근접하는 합성가스를 제조하기 곤란할 수 있다. According to a preferred aspect of the present invention, the reforming catalyst (NiO-La / Ce-ZrO 2 / Al 2 O 3) is a supported nickel to 5-20% by weight of lanthanum and cerium in the formula, zirconia / alumina support. It may be difficult to produce a synthesis gas in which the molar ratio of hydrogen to 1 mole of carbon monoxide is close to 2 when the supported amount is out of the above range.
본 발명의 바람직한 실시예에 의하면, 상기 개질촉매는 란탄과 세륨의 중량비가 1: 2 ~ 10 일 수 있다. 상기 범위를 벗어나면 일산화탄소 1몰에 대한 수소의 몰비가 2에 근접하는 합성가스를 제조하기 곤란할 수 있다. According to a preferred embodiment of the present invention, the weight ratio of lanthanum to cerium may be 1: 2 to 10 in the reforming catalyst. If it is out of the above range, it may be difficult to produce a synthesis gas in which the molar ratio of hydrogen to 1 mole of carbon monoxide is close to 2.
본 발명은 또한 상기 촉매를 사용하여 반응온도 700 ~ 950 ℃, 반응압력 10 ~ 20 bar, 공간속도 3000 ~ 4000 h-1의 조건으로 이산화탄소, 수증기 및 메탄을 공급하여 개질반응을 수행하는 것을 특징으로 하는 합성가스의 제조방법을 제공한다. 메탄 1몰에 대하여 이산화탄소 0.4 ~ 1 몰비, 수증기 1 ~ 3 몰비로 공급하는 것이 바람직하다. 이러한 개질반응을 통하여 제조된 합성가스의 일산화탄소 1몰에 대한 수소의 몰비가 2.0±0.2이므로 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 a reaction temperature of 700 to 950 ° C, a reaction pressure of 10 to 20 bar, and a space velocity of 3000 to 4000 h -1 , The synthesis gas being produced by the synthesis gas. It is preferable to supply carbon dioxide in a molar ratio of 0.4 to 1 mole of 1 mole of methane and 1 to 3 mole of water vapor. Since the molar ratio of hydrogen to 1 mole of carbon monoxide produced through the reforming reaction is 2.0 + - 0.2, synthetic gas which is efficient in producing synthetic petrochemical products (wax, naphtha, diesel, etc.) can be easily provided.
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 란탄 및 세륨으로 수식된 지르코니아/알루미나 담체상에 니켈 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 catalyst used in the conventional steam-carbon dioxide reforming reaction, the deactivation of the catalyst is observed or the activity is lowered at a high space velocity. On the other hand, in the case of the nickel-reforming catalyst used in the present invention, a certain amount of nickel metal is supported on a zirconia / alumina carrier modified with lanthanum and cerium to prepare a nickel-reforming catalyst, A synthesis gas which is a mixture of carbon monoxide and hydrogen can be produced at a high yield.
본 발명에 따른 메탄 천연가스의 수증기-이산화탄소 개질반응에 사용하는 니켈 개질 촉매는 란탄 및 세륨 수식된 지르코니아/알루미나 담체 내에 활성성분인 니켈이 5 ~ 20 중량% 로 담지된 개질촉매(NiO-La/Ce-ZrO2/Al2O3)인 것이 바람직하다. 니켈의 담지량이 상기 범위를 벗어나 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 in the steam-carbon dioxide reforming reaction of methane natural gas according to the present invention is a reforming catalyst (NiO-La / Al 2 O 3) in which nickel as an active ingredient is supported in a lanthanum and cerium-modified zirconia / that the Ce-ZrO 2 / Al 2 O 3) is preferred. If the loading amount of nickel is out of the above range and less than 5 wt%, there is a problem of low activity. If the loading amount of nickel exceeds 20 wt%, deactivation of the catalyst due to deposition of coke occurs, which is not preferable.
이때, 담체로서 사용된 란탄 및 세륨이 수식된 지르코니아/알루미나 담체는 지르코니아/알루미나와 란탄 및 세륨이 혼성되어 있는 것으로 란탄(La) 및 세륨(Ce)의 중량비가 1: 2 ~ 10 범위로 함유되며, 란탄 및 세륨의 함량이 상기 범위를 초과하여 과량으로 수식되면 촉매의 활성이 낮아지는 문제가 있다. At this time, the lanthanum and cerium-modified zirconia / alumina carrier used as the carrier is a mixture of zirconia / alumina, lanthanum and cerium, and contains lanthanum (La) and cerium (Ce) in a weight ratio of 1: 2 to 10 , Lanthanum and cerium exceeding the above range and being excessively modified, there is a problem that the activity of the catalyst is lowered.
본 발명에 따른 니켈계 개질촉매를 제조함에 있어서 지르코니아계/알루미나 담체에 란탄 및 세륨을 수식하는 방법이나 니켈을 담지하는 방법은 건식 또는 습식 혼합 후 건조, 반죽, 압출, 소성하는 방법을 사용한다. 용매는 증류수를 사용하는 것이 바람직하다. In the preparation of the nickel-based reforming catalyst according to the present invention, a method of modifying lanthanum and cerium on a zirconia-based / alumina carrier or a method of supporting nickel is dry or wet mixed, followed by drying, kneading, extrusion and firing. As the solvent, it is preferable to use distilled water.
가장 바람직하게는 원하는 비율로 산화란탄(La2O3), 세리아, 지르코니아, 산화니켈, 알루미나를 혼합시킴으로써 란탄 및 세륨으로 수식된 지르코니아/알루미나 담체를 얻을 수 있다. Most preferably, it is possible to obtain a zirconia / alumina carrier modified with cerium, and lanthanum by mixing a lanthanum oxide (La 2 O 3), ceria, zirconia, nickel oxide and alumina in a desired ratio.
또한, 니켈산화물의 파우더 형태를, 란탄 및 세륨으로 수식된 지르코니아/알루미나 담체와 함께 혼합하여 반죽 및 압출후 소성하는 과정을 거친다. 소성은 700 ~ 1200 ℃의 온도에서 공기 중에서 5 ~ 8 시간 실시하는 것이 바람직하다. Further, the powder form of the nickel oxide is mixed with the zirconia / alumina carrier modified with lanthanum and cerium, followed by kneading, extrusion, and firing. The firing is preferably performed at a temperature of 700 to 1200 DEG C for 5 to 8 hours in air.
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, a typical fixed-bed catalytic reactor prepared in a laboratory is used for measuring the reforming activity of the catalyst. Then, the catalyst is shaped and crushed to have a particle size of 1 to 2 mm by a pretreatment process before the reaction, and the catalyst is filled in the reactor by the required amount and then reduced with 5% hydrogen at 700 ° C for 1 hour before the reaction.
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 ~ 950 ℃의 범위로 조절되며, 반응압력은 10 ~ 20 기압이고, 공간속도가 3000 ~ 4000 hr-1의 조건이 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 as reactants are fed into the reactor at a molar ratio of 1: 1 to 3: 3, carbon dioxide: 0.4 to 1, and nitrogen is added as a diluent if necessary. At this time, the temperature of the reactor is adjusted to a range of 700 ~ 950 ℃ by an electric heater and the program thermostat possible, and the reaction pressure is preferably from 10 to 20 atmospheric pressure, and space velocity is such that the mass conditions of 3000-4000 hr -1 Syngas can be produced by injecting gas while continuously controlling the gas flow rate with a mass flow controller. The composition of the gas before and after the reaction is analyzed by a gas chromatograph directly connected to the reaction apparatus, and a poropak column is used for gas separation.
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 order to measure the activity and thermal stability of the reforming catalyst in the above manner, the activity was measured at 750 ° C. over time, and the activity after 200 minutes and the initial activity were calculated from the yield of hydrogen and the conversion of methane .
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 a syngas from natural gas using the reforming catalyst according to the present invention shows better activity than the activity of a conventional zirconia-supported nickel-reforming catalyst and can maintain high activity even at a high gas space velocity Therefore, it is possible to use the catalyst 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 with reference to the following examples, but the present invention is not limited to the examples.
제조예 1Production Example 1
알루미나, 세리아, 지르코니아, 산화니켈, 산화란탄을 파우더형태로 표1과 같은 비율로 섞고 증류수를 넣고 교반기를 이용하여 교반하여 잘 혼합한 후 건조시킨다. 충분히 혼합한 후 3℃/min의 속도로 700~950℃까지 승온하여 6시간 동안 소성시켜 촉매를 얻었다. Alumina, ceria, zirconia, nickel oxide, and lanthanum oxide are mixed in powder form in the same ratio as in Table 1, mixed with distilled water, stirred using a stirrer, mixed well and dried. After thoroughly mixing, the mixture was heated to 700 to 950 ° C at a rate of 3 ° C / min and calcined for 6 hours to obtain a catalyst.
제조예 2Production Example 2
알루미나에 세리아, 지르코니아를 건조된 파우더형태로 넣고 볼밀링을 하여 혼합시킨다. 또한, 산화니켈, 산화란탄, 알루미나를 같은 방식으로 혼합한 후 두 파우더를 혼합한 후 700~950℃에서 6시간동안 소성하여 NiO-La/Ce-ZrO2/Al2O3을 얻을 수 있다.Ceria and zirconia are added to the alumina in the form of dried powder and mixed by ball milling. In addition, NiO-La / Ce-ZrO 2 / Al 2 O 3 can be obtained by mixing nickel oxide, lanthanum oxide and alumina in the same manner and then mixing the two powders and calcining at 700 to 950 ° C. for 6 hours.
실시예Example 1 내지 5 1 to 5
제조예 1에서 제조한 촉매 7g 사용하여 SCR 공정(Steam Carbon dioxide Reforming)에 적용하였다. 운전조건은 온도 700 ~ 950℃, 압력 18 bar를 유지하였으며. 수증기, 이산화탄소, 메탄의 주입 유량을 하기 표 3과 같이 변경하여 3000 ~ 4000hr-1의 공간속도로 메탄의 개질반응을 수행하였다. 주입된 가스의 비율과 반응결과는 아래 표 3, 도 1 및 도 2와 같다.
Was applied to the SCR process (Steam Carbon dioxide Reforming) using 7 g of the catalyst prepared in Preparation Example 1. The operating conditions were maintained at a temperature of 700 ~ 950 ℃ and a pressure of 18 bar. The reforming reaction of methane was performed at a space velocity of 3000 to 4000 hr -1 by changing the injection flow rate of steam, carbon dioxide, and methane as shown in Table 3 below. The ratio of the injected gas and the reaction result are shown in Table 3, Fig. 1 and Fig. 2 below.
상기 결과로부터, 공급가스의 범위를 1 : 0.4~1 : 1~3의 범위 내에서 변경하였을 때 메탄 전환율을 90% 이상을 유지하였고 합성가스의 비율 1.9~2.4를 만족하는 합성가스를 제조할 수 있음을 알 수 있다.
From the above results, it can be seen that when the range of the feed gas is changed within the range of 1: 0.4 to 1: 1 to 3, a synthesis gas having a methane conversion rate of 90% or more and a synthesis gas ratio of 1.9 to 2.4 can be produced .
실시예 6 내지 10Examples 6 to 10
제조예 2에서 제조한 촉매를 사용하여 실시예 1과 동일한 조건으로 개질반응을 수행하였다. 결과는 하기 표 4에 나타내었다.
Using the catalyst prepared in Preparation Example 2, a reforming reaction was carried out under the same conditions as in Example 1. The results are shown in Table 4 below.
제조예 2의 촉매를 사용한 경우에도, 공급가스의 범위를 1 : 0.4~1 : 1~3의 범위 내에서 변경하였을 때 메탄전환율을 95% 이상을 유지하였고 합성가스의 비율 1.9~2.2를 만족하는 합성가스를 제조할 수 있었다.
Even when the catalyst of Production Example 2 was used, when the range of the feed gas was changed within the range of 1: 0.4 to 1: 1 to 3, the methane conversion rate was maintained at 95% or more and the ratio of the synthesis gas was 1.9 to 2.2 Synthesis gas could be produced.
비교예Comparative Example 1 One
함침법을 이용하고 활성성분으로서 Ni을 지지체 Ce-Zr/MgAlOx 에 담지한 촉매(한국특허 출원 제2008-0075787호)를 사용하여 700 ~ 950℃, 압력 18bar의 반응 조건에서 혼합 개질반응을 수행한 결과는 표 5와 같다. A mixed reforming reaction was carried out at 700 to 950 ° C under a reaction pressure of 18 bar using a catalyst (Korean Patent Application No. 2008-0075787) carrying Ni as an active ingredient on a support Ce-Zr / MgAlOx using an impregnation method The results are shown in Table 5.
상기 결과로부터, 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 설계 시 1/3 ~ 1/5의 용량으로 같은 CH4 전환율을 나타낼 수 있다는 것, 즉 경제성이 높다는 것을 의미한다. From the above results, it can be seen that the catalysts of the examples are much larger than those of the comparative examples, when comparing the space velocity representing the equivalent level of methane conversion. This means that the size of the reactor can be minimized, so that it is possible to exhibit the same CH 4 conversion rate in the capacity of 1/3 to 1/5 in the design of the commercialization reactor, that is, the economy is high.
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 생성되는 CO2를 다량 회수할 수 있어 타 공정보다 CO2 처리능력이 높다는 장점이 있다.Further, when the catalyst of the embodiment is used, CO 2 It can be seen that the content can be increased more than twice as compared with the comparative example. Therefore, it is advantageous to use a gas having a high CO 2 content in the reaction gas, and it is possible to recover a large amount of CO 2 produced after the reaction, which is advantageous in that CO 2 treatment ability is higher than other processes.
Claims (10)
2) 단계 1)의 담체 분말과 니켈 분말을 혼합하여 소성하는 단계를 포함하는 방법에 의해 제조된, 합성가스를 제조하기 위한 개질반응용 촉매.
1) preparing a zirconia and alumina carrier modified with lanthanum and cerium in a wet or dry ball mill manner;
2) A catalyst for reforming reaction for producing synthesis gas, which is produced by a method comprising mixing and calcining a support powder of step 1) and a nickel powder.
상기 개질반응은 수증기-이산화탄소 개질반응인 것을 특징으로 하는 개질반응용 촉매.
The method according to claim 1,
Wherein the reforming reaction is a steam-carbon dioxide reforming reaction.
상기 개질반응용 촉매는 란탄 및 세륨 수식된 지르코니아/알루미나 담체(La, Ce-ZrO2/Al2O3) 내에 란탄이 1 ~ 7 중량% 함유된 것을 특징으로 하는 개질반응용 촉매.
The method according to claim 1,
Wherein the catalyst for reforming reaction contains 1 to 7% by weight of lanthanum in a lanthanum and cerium-modified zirconia / alumina carrier (La, Ce-ZrO 2 / Al 2 O 3 ).
상기 단계 2)의 소성은 700 ~ 1200℃의 온도에서 공기 중에서 실시하는 것을 특징으로 하는 개질반응용 촉매.
The method according to claim 1,
Wherein the calcination of step 2) is carried out in air at a temperature of 700 to 1200 ° C.
상기 단계 2)의 혼합은 건식 볼밀 또는 습식혼합한 후 건조하여 반죽 및 압출하는 과정을 포함하는 것을 특징으로 하는 개질반응용 촉매.
The method according to claim 1,
Wherein the mixing of step 2) comprises dry ball milling or wet mixing followed by drying and kneading and extruding.
상기 개질반응용 촉매는 란탄 및 세륨 수식된 지르코니아/알루미나 담체(La, Ce-ZrO2/Al2O3) 내에 니켈이 5 ~ 20 중량% 담지된 것을 특징으로 하는 개질반응용 촉매.
The method according to claim 1,
Wherein the catalyst for reforming reaction contains 5-20 wt% of nickel in a lanthanum and cerium-modified zirconia / alumina carrier (La, Ce-ZrO 2 / Al 2 O 3 ).
상기 개질반응용 촉매는 란탄과 세륨의 중량비가 1: 2 ~ 10 인 것을 특징으로 하는 개질반응용 촉매.
The method according to claim 1,
Wherein the catalyst for reforming reaction has a weight ratio of lanthanum and cerium of 1: 2 to 10.
A process for producing a reformed catalyst by supplying carbon dioxide, steam and methane under the conditions of a reaction temperature of 700 to 950 ° C, a reaction pressure of 10 to 20 atm, and a space velocity of 3000 to 4000 h -1 using the catalyst of any one of claims 1 to 7, ≪ / RTI >
The method according to claim 8, wherein carbon monoxide is supplied at a molar ratio of carbon dioxide of 0.4 to 1, and water vapor of 1 to 3 to 1 mole of methane.
상기 개질반응을 통하여 제조된 합성가스는 일산화탄소 1몰에 대한 수소의 몰비가 2.0±0.2인 것을 특징으로 하는 방법. 9. The method of claim 8,
Wherein the synthesis gas produced through the reforming reaction has a molar ratio of hydrogen to 1 mole of carbon monoxide of 2.0 +/- 0.2.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120144030A KR101401170B1 (en) | 2012-12-12 | 2012-12-12 | Lanthanum containing catalysts for preparing syn-gas by steam-carbon dioxide reforming reaction and process for preparing syn-gas using same |
| PCT/KR2013/011531 WO2014092482A1 (en) | 2012-12-12 | 2013-12-12 | Catalyst containing lanthanum for manufacturing synthetic gas through steam-carbon dioxide reforming, and method for manufacturing synthetic gas by using same |
| MYPI2015001516A MY169114A (en) | 2012-12-12 | 2013-12-12 | Lanthanum-containing catalyst for syngas production by steam-carbon dioxide reforming and method for syngas production using same |
| CN201380071806.3A CN104955564A (en) | 2012-12-12 | 2013-12-12 | Catalyst containing lanthanum for manufacturing synthetic gas through steam-carbon dioxide reforming, and method for manufacturing synthetic gas by using same |
| AU2013360537A AU2013360537B2 (en) | 2012-12-12 | 2013-12-12 | Catalyst containing lanthanum for manufacturing synthetic gas through steam-carbon dioxide reforming, and method for manufacturing synthetic gas by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120144030A KR101401170B1 (en) | 2012-12-12 | 2012-12-12 | Lanthanum containing catalysts for preparing syn-gas by steam-carbon dioxide reforming reaction and process for preparing syn-gas using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR101401170B1 true KR101401170B1 (en) | 2014-05-29 |
Family
ID=50895765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020120144030A KR101401170B1 (en) | 2012-12-12 | 2012-12-12 | Lanthanum containing catalysts for preparing syn-gas by steam-carbon dioxide reforming reaction and process for preparing syn-gas using same |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR101401170B1 (en) |
| CN (1) | CN104955564A (en) |
| AU (1) | AU2013360537B2 (en) |
| MY (1) | MY169114A (en) |
| WO (1) | WO2014092482A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413734A (en) * | 2015-12-07 | 2016-03-23 | 西南化工研究设计院有限公司 | Nickel-based catalyst for preparing reducing gas by reforming methane-carbon dioxide and preparation method of nickel-based catalyst |
| WO2017090864A1 (en) * | 2015-11-24 | 2017-06-01 | 한국화학연구원 | Cobalt-supported catalyst for low-temperature reforming reaction and production method therefor |
| KR101761829B1 (en) * | 2015-05-07 | 2017-07-26 | 성균관대학교산학협력단 | Preparing method of synthesis gas and carbon monoxide |
| KR20180115113A (en) * | 2017-04-12 | 2018-10-22 | (주)바이오프랜즈 | Chemical Production and Power Generation System using Landfill Gas |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080043161A (en) * | 2006-11-13 | 2008-05-16 | 고려대학교 산학협력단 | Supported catalyst for producing hydrogen gas by steam reforming reaction of liquefied natural gas, method for preparing the supported catalyst and method for producing hydrogen gas using the supported catalyst |
| KR20100065504A (en) * | 2008-12-08 | 2010-06-17 | 한국화학연구원 | Preparation method of methanol through synthesis gas derived from the combined reforming of natural gas and carbon dioxide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3761947B2 (en) * | 1995-11-08 | 2006-03-29 | 石油資源開発株式会社 | Catalyst composition for producing synthesis gas and method for producing synthesis gas using the same |
| CN101637726A (en) * | 2008-07-31 | 2010-02-03 | 中国石油天然气股份有限公司 | Method for preparing catalyst for preparing synthesis gas by reforming methane and carbon dioxide |
| CN101352687B (en) * | 2008-08-29 | 2011-09-14 | 同济大学 | Catalyst for carbon dioxide dry-reforming of methane, and preparation method and use thereof |
-
2012
- 2012-12-12 KR KR1020120144030A patent/KR101401170B1/en active IP Right Grant
-
2013
- 2013-12-12 AU AU2013360537A patent/AU2013360537B2/en active Active
- 2013-12-12 WO PCT/KR2013/011531 patent/WO2014092482A1/en active Application Filing
- 2013-12-12 MY MYPI2015001516A patent/MY169114A/en unknown
- 2013-12-12 CN CN201380071806.3A patent/CN104955564A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080043161A (en) * | 2006-11-13 | 2008-05-16 | 고려대학교 산학협력단 | Supported catalyst for producing hydrogen gas by steam reforming reaction of liquefied natural gas, method for preparing the supported catalyst and method for producing hydrogen gas using the supported catalyst |
| KR20100065504A (en) * | 2008-12-08 | 2010-06-17 | 한국화학연구원 | Preparation method of methanol through synthesis gas derived from the combined reforming of natural gas and carbon dioxide |
Non-Patent Citations (2)
| Title |
|---|
| Applied Ctlysis A: General, Vol.385, 2010, pp.92-100 * |
| Korean J. Chem.Eng., Vol.19(5), pp.742-748, 2002 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101761829B1 (en) * | 2015-05-07 | 2017-07-26 | 성균관대학교산학협력단 | Preparing method of synthesis gas and carbon monoxide |
| WO2017090864A1 (en) * | 2015-11-24 | 2017-06-01 | 한국화학연구원 | Cobalt-supported catalyst for low-temperature reforming reaction and production method therefor |
| KR101825495B1 (en) | 2015-11-24 | 2018-02-05 | 한국화학연구원 | Cobalt-supported catalyst for low-temperature methane reformation using carbon dioxide, and the fabrication method thereof |
| CN105413734A (en) * | 2015-12-07 | 2016-03-23 | 西南化工研究设计院有限公司 | Nickel-based catalyst for preparing reducing gas by reforming methane-carbon dioxide and preparation method of nickel-based catalyst |
| KR20180115113A (en) * | 2017-04-12 | 2018-10-22 | (주)바이오프랜즈 | Chemical Production and Power Generation System using Landfill Gas |
| KR102488300B1 (en) * | 2017-04-12 | 2023-01-13 | (주)바이오프랜즈 | Chemical Production and Power Generation System using Landfill Gas |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2013360537B2 (en) | 2016-05-12 |
| AU2013360537A1 (en) | 2015-07-16 |
| CN104955564A (en) | 2015-09-30 |
| WO2014092482A1 (en) | 2014-06-19 |
| MY169114A (en) | 2019-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8834835B2 (en) | Ultra high temperature shift catalyst with low methanation | |
| US7226548B2 (en) | Syngas catalysts and their method of use | |
| US6878667B2 (en) | Nickel-rhodium based catalysts for synthesis gas production | |
| EP1093852B1 (en) | Process for the autothermal reforming of hydrocarbon feedstock | |
| KR101421825B1 (en) | Catalysts for preparing syn-gas by steam-carbon dioxide reforming reaction and process for preparing syn-gas using same | |
| KR101298783B1 (en) | Process for the preparation of fisher-tropsch catalysts | |
| KR20100014012A (en) | Catalyst for the preparation of synthesis gas from natural gas with carbon dioxide and the preparation method there of | |
| WO2007029862A1 (en) | Catalyst for catalytic partial oxidation of hydrocarbon and process for producing synthesis gas | |
| KR101595181B1 (en) | Process for the preparation of fisher-tropsch catalysts having improved activity and life time | |
| WO2005051527A2 (en) | Copper-modified catalysts for oxidative dehydrogenation | |
| KR101437072B1 (en) | Catalyst for efficient co2 conversion and method for preparing thereof | |
| KR101401170B1 (en) | Lanthanum containing catalysts for preparing syn-gas by steam-carbon dioxide reforming reaction and process for preparing syn-gas using same | |
| EP3256249A1 (en) | Use of nickel-manganese olivine and nickel-manganese spinel as bulk metal catalysts for carbon dioxide reforming of methane | |
| KR101480801B1 (en) | Monolith type reforming catalyst, preparation method thereof and process for syn gas | |
| Zhang et al. | CO 2 Conversion to Value‐Added Gas‐Phase Products: Technology Overview and Catalysts Selection | |
| KR100336968B1 (en) | Modified Zirconia-supported nickel reforming catalysts and its use for producing synthesis gas from natural gas | |
| JP4759242B2 (en) | Synthesis gas production catalyst and synthesis gas production method using the same | |
| WO2010135297A1 (en) | Ultra high temperature shift catalyst with low methanation | |
| KR100390774B1 (en) | The preparation method of synthesis gas from natural gas by oxygen or steam-oxygen mixed reforming | |
| KR20150129566A (en) | Ni-based catalysts for combined steam and carbon dioxide reforming with natural gas | |
| KR101440193B1 (en) | Catalyst for the mixed reforming of natural gas, preparation method thereof and method for mixed reforming of natural gas using the catalyst | |
| KR100732729B1 (en) | Ni-based Catalyst for Tri-reforming of Methane and Its Catalysis Application for the Production of Syngas | |
| KR102142686B1 (en) | Bilayered catalytic reactor and system for producing the synthesis gas using the same | |
| KR101533537B1 (en) | Catalyst platinum loaded in the mixed oxide support comprising ceria-zirconia for aqueous phase reforming | |
| KR20240080539A (en) | Catalyst for dry reforming reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20170412 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20180403 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20190326 Year of fee payment: 6 |