KR20060007574A - Hydrogen Production Method Using Membrane Reactor - Google Patents
Hydrogen Production Method Using Membrane ReactorDownload PDFInfo
- Publication number
- KR20060007574A KR20060007574AKR1020040056403AKR20040056403AKR20060007574AKR 20060007574 AKR20060007574 AKR 20060007574AKR 1020040056403 AKR1020040056403 AKR 1020040056403AKR 20040056403 AKR20040056403 AKR 20040056403AKR 20060007574 AKR20060007574 AKR 20060007574A
- Authority
- KR
- South Korea
- Prior art keywords
- hydrogen
- reaction
- dme
- membrane
- membrane reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
- C01B3/505—Membranes containing palladium
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
- C01B2203/041—In-situ membrane purification during hydrogen production
- 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
- C01B2203/1076—Copper or zinc-based catalysts
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Translated fromKoreanDescription
Translated fromKorean도 1은 디메틸에테르(DME)를 수증기 개질하여 수소를 제조하는 장치의 개략도이다.1 is a schematic diagram of an apparatus for producing hydrogen by steam reforming dimethyl ether (DME).
[도 1의 공정 설계도의 주요 부분에 대한 부호의 설명][Explanation of the code | symbol about the principal part of the process blueprint of FIG. 1]
1 : He 가스 2 : 디메틸에테르(DME)1: He gas 2: Dimethyl ether (DME)
3 : H2O 4 : 질량 유속 조절기3: H2 O 4: mass flow regulator
5 : 액체 펌프 6 : 온도 조절기5: liquid pump 6: thermostat
7 : 열전대 온도계 8 : 연소로7: thermocouple thermometer 8: combustion furnace
9 : 분리막 반응기 10 : 냉각조9: membrane reactor 10: cooling tank
11 : 습도 트랩 12 : 샘플 벨브11: Humidity Trap 12: Sample Valve
13 : 가스크로마토그래피 14 : 기준컬럼13: gas chromatography 14: reference column
15 : 분석컬럼15: Analysis column
본 발명은 분리막 반응기를 이용한 수소의 제조방법에 관한 것으로서, 보다 상세하게는 촉매 존재하에서 디메틸에테르로부터 수소를 제조함에 있어 반응과 동시에 분리의 수행 가능한 분리막 반응기를 적용하여, 반응 생성물인 수소와 부생성물인 일산화탄소, 이산화탄소, 메탄 및 미반응된 DME의 선택적인 분리가 가능하고, DME의 전환율을 증가시킬 뿐만 아니라 부생성물의 생성을 억제하여 높은 반응 효율을 얻을 수 있으며, 또한 별도의 분리 공정을 생략할 수 있는 효과를 동시에 얻을 수 있는 분리막 반응기를 이용한 수소의 제조방법에 관한 것이다.The present invention relates to a method for producing hydrogen using a membrane reactor, and more particularly, in the production of hydrogen from dimethyl ether in the presence of a catalyst by applying a membrane reactor capable of performing the reaction and separation at the same time, the reaction product hydrogen and by-products It is possible to selectively separate phosphorus carbon monoxide, carbon dioxide, methane and unreacted DME, and to increase the conversion rate of DME as well as to suppress the formation of by-products to obtain high reaction efficiency, and also to omit a separate separation process. It relates to a method for producing hydrogen using a membrane reactor that can attain the same effect.
일반적으로 연료전지는 탄화수소 계열 연료에 포함되어 있는 탄소 또는 수소와 공기중의 산소를 전기화학 반응으로 직접 전기 에너지로 변환시키는 고효율의 청정 발전기술이다.In general, a fuel cell is a high-efficiency clean power generation technology that converts carbon or hydrogen contained in a hydrocarbon-based fuel and oxygen in the air directly into electrical energy through an electrochemical reaction.
연료전지의 연료로 메탄, 메탄올, 가솔린 등의 탄화수소 계열을 수증기 개질하여 수소를 제조하는 방법은 널리 알려져 있으며, 이는 편리한 유용성, 높은 에너지 밀도, 저장과 수송의 용이성 등의 장점이 있으나, 독성이 큰 것이 단점으로 지적되고 있다. 또한, 가솔린의 경우는 반응의 기반구조는 잘 갖춰져 있지만 수증기 개질 반응이 800 ℃ 근처의 고온에서 진행되고, 함유된 황이 촉매독으로 작용하여 반응이 용이하지 못한 문제가 있다.Hydrogen is produced by steam reforming a hydrocarbon series such as methane, methanol, gasoline, etc. as fuel of a fuel cell, which has advantages such as convenient usability, high energy density, and ease of storage and transportation. It is pointed out as a disadvantage. In addition, in the case of gasoline, although the reaction infrastructure is well established, the steam reforming reaction proceeds at a high temperature near 800 ° C, and the sulfur contained acts as a catalyst poison, making the reaction difficult.
최근에는 각종 환경오염을 유발하는 화석연료를 대체하는 청정연료로 무독성이고, 환경 친화적인 성질로 인하여 오존층 파괴의 주범인 트리클로로플루오로에탄 (CFC)을 대체하여 에어로졸 분사제로 사용되고 있는 디메틸에테르(DME)에 대한 연구가 집중적으로 이루어지고 있다.Recently, dimethyl ether (DME) has been used as an aerosol propellant by replacing trichlorofluoroethane (CFC), which is the main cause of ozone depletion, because it is a clean fuel that replaces fossil fuels causing various environmental pollution. ) Is being intensively studied.
이러한 디메틸에테르(DME)는 상온에서도 쉽게 액화가 가능하고, 액화 석유 가스(LPG)와 물리적 성질이 유사하여 유통 및 보급체계를 그대로 사용할 수 있는 장점을 가지고 있으며, 황을 함유하고 있지 않아 수증기 개질반응이 용이하여 탈화 설비가 필요하지 않아 설비비용을 줄일 수 있어 이상적인 수소제조용 원료이다. 또한 상업화 되어있는 기존의 개질반응 공정에 그대로 적용할 수 있으며, 무엇보다 기존의 수소원료보다 수소 발생을 위한 수증기 개질반응의 반응열이 낮아 에너지 비용을 줄일 수 있는 장점을 가지고 있다.This dimethyl ether (DME) can be easily liquefied even at room temperature, and the physical properties similar to liquefied petroleum gas (LPG) has the advantage of using the distribution and distribution system as it is, and does not contain sulfur, steam reforming reaction This is an ideal raw material for producing hydrogen because it is easy to reduce the equipment cost since no desalination equipment is required. In addition, it can be applied to the existing reforming process that is commercialized, and above all, the heat of steam reforming reaction for generating hydrogen is lower than conventional hydrogen raw materials, which has the advantage of reducing energy costs.
이에 촉매 존재하에서 디메틸에테르(DME)를 수증기 개질하여 수소를 생산하는 기술은 소개된 바[대한민국 특허등록 제0373620호]있으나, 연료전지에 있어 탄소산화물의 억제가 필수적이나 수소와 함께 부생성물인 탄소산화물도 제조되는 단점이 있다.Therefore, a technique for producing hydrogen by steam reforming dimethyl ether (DME) in the presence of a catalyst has been introduced (Korean Patent Registration No. 0373620). However, suppression of carbon oxides is essential in fuel cells, but carbon, which is a by-product of hydrogen, is a byproduct. Oxides also have drawbacks.
이에 본 발명자는 디메틸에테르(DME)의 수증기 개질 반응으로부터 생성되는 탄소산화물을 억제하면서 막에 의해 수소만을 선택적으로 투과시킴으로써 전환율을 향상시키고자 연구 노력한 결과, 촉매 존재 하에서 반응과 분리를 결합한 분리막 반응기를 도입하여 수소의 생성과 동시에 선택적으로 분리할 수 있어 완화된 반응조건에서 반응효율을 향상시키고, 일산화탄소의 생성을 억제하며, 별도의 분리공정 을 생략하여 경제적임을 알게 되어 본 발명을 완성하게 되었다.Therefore, the present inventors have tried to improve the conversion rate by selectively permeating hydrogen only through the membrane while suppressing the carbon oxide generated from the steam reforming reaction of dimethyl ether (DME). By introducing hydrogen can be selectively separated at the same time to improve the reaction efficiency in the relaxed reaction conditions, to suppress the production of carbon monoxide, omitted a separate separation process to realize the economics to complete the present invention.
따라서, 본 발명은 촉매 존재하에서 디메틸에테르(DME)를 수증기 개질 반응시켜 수소를 제조하는 방법에 있어서, 반응과 동시에 수소 기체를 부생성물 및 미 반응물과 선택적으로 분리하여 공정을 단순화시킬 뿐만 아니라 막에 의해 수소 기체만을 선택적으로 투과시킴으로써 반응 전환율을 향상시킬 수 있는 분리막 반응기를 이용한 수소의 제조방법을 제공하는데 그 목적이 있다.
Accordingly, the present invention provides a method for producing hydrogen by steam reforming dimethyl ether (DME) in the presence of a catalyst, which simultaneously simplifies the process by selectively separating hydrogen gas from by-products and unreacted materials as well as the reaction. It is an object of the present invention to provide a method for producing hydrogen using a membrane reactor which can improve the reaction conversion rate by selectively permeating only hydrogen gas.
본 발명은 촉매 존재하에서 디메틸에테르(DME)를 수증기 개질 반응시켜 수소를 제조하는 방법에 있어서, 수소기체 분리막이 장착되어 있고, 200 ∼ 500 ℃의 온도와 30 ∼ 500 ㎪ 압력이 유지되는 막반응기내에서 디메틸에테르를 수증기 개질 반응시킴과 동시에 생성된 혼합기체로부터 수소만을 분리 수득하는 분리막 반응기를 이용한 수소의 제조방법에 그 특징이 있다.The present invention relates to a method for producing hydrogen by steam reforming dimethyl ether (DME) in the presence of a catalyst, wherein the membrane is equipped with a hydrogen gas separation membrane and maintained at a temperature of 200 to 500 ° C. and a pressure of 30 to 500 kPa. There is a feature of the hydrogen production method using a membrane reactor for steam and dimethyl ether reforming at the same time to separate and obtain only hydrogen from the resulting mixed gas.
이와 같은 발명을 더욱 상세히 설명하면 다음과 같다.When explaining the invention in more detail as follows.
본 발명은 디메틸에테르(DME)의수증기 개질 반응에 의해 수소를 제조함에 있어서, 반응과 분리를 동시에 수행할 수 있는 분리막 반응기를 적용하여 반응과 동시에 생성물인 수소와 함께 부생성물인 일산화탄소, 이산화탄소, 메탄 및 미반응된 DME을 선택적으로 분리하고, DME의 전환율을 증가시킬 뿐만 아니라 부생성물의 생성을 억제하여 높은 반응 효율을 얻을 수 있으며, 별도의 분리 공정을 생략할 수 있는 디메틸에테르(DME)로부터 수소를 제조하는 방법에 관한 것이다. 특히, 순 수한 수소를 선택적으로 분리해 낼 수 있으므로 연료전지 분야에 유용할 것으로 기대된다.In the present invention, in the production of hydrogen by the steam reforming reaction of dimethyl ether (DME), by applying a membrane reactor that can perform the reaction and separation at the same time by-product carbon monoxide, carbon dioxide, methane as a by-product along with the reaction And selectively separating unreacted DME, increasing the conversion rate of DME as well as inhibiting the formation of by-products to obtain high reaction efficiency, and hydrogen from dimethyl ether (DME), which can separate a separate separation process. It relates to a method of manufacturing. In particular, it is expected to be useful in the fuel cell field because it can selectively separate pure hydrogen.
기존의 디에틸에테르로부터 수소 제조시 300 ∼ 900 ℃ 정도의 온도조건에서 수증기 개질 반응이 수행되는 것으로 알려져 있으나 실제로는 800 ℃ 정도의 고온에서 수행되고 있어, 상기 고온으로 인한 반응수율 저하 및 공정상의 제어 위험성 등의 문제가 있었으며, 또한 반응 후 수소를 별도의 방법으로 분리시키는 공정이 추가로 요구되었으며, 분리 과정에서 수소의 손실 및 결여 등으로 경제성에 문제가 있었다. 이에 본 발명은 하나의 반응기내에서 수증기 개질 반응 및 수소분리 수득을 동시에 수행하도록 하기 위하여 수소기체 분리막을 장착시긴 새로운 개념의 막반응기를 제시한다. 또한 본 발명은 상기 막반응기의 도입 이외에 실제 고온에서 수행되던 반응 조건을 200 ∼ 500 ℃의 온도와 30 ∼ 500 ㎪ 압력 범위의 온화한 조건에서 반응 수행이 가능하여 상기 고온으로 인한 문제까지 추가적으로 해결하는 효과까지 발휘하는 효과적인 것이다.It is known that steam reforming reaction is carried out at a temperature of about 300 to 900 ° C. when hydrogen is produced from conventional diethyl ether, but is actually performed at a high temperature of about 800 ° C., resulting in a decrease in reaction yield and process control. There was a problem such as risk, and further required to separate the hydrogen by a separate method after the reaction, there was a problem in economics due to the loss and lack of hydrogen in the separation process. Accordingly, the present invention proposes a new concept membrane reactor equipped with a hydrogen gas separation membrane in order to simultaneously carry out steam reforming reaction and hydrogen separation in one reactor. In addition, the present invention is capable of performing the reaction under mild conditions of the temperature range of 200 ~ 500 ℃ and pressure range of 30 ~ 500 ℃ in addition to the introduction of the membrane reactor at the actual high temperature effect to further solve the problem due to the high temperature It will be effective until.
본 발명을 다음 도 1에 나타낸 공정 장치를 이용하여 보다 구체적으로 살펴보면 다음과 같다.Looking at the present invention in more detail using the process equipment shown in Figure 1 as follows.
본 발명의 공정 장치는 He 가스(1), 디메틸에테르(DME)(2), H2O(3), 질량 유속 조절기(4), 액체 펌프(5)의 공급부; 온도 조절기(6), 열전대(7), 연소로(8), 분리막 반응기(9)의 반응 및 분리부; 및 냉각조(10), 습도 트랩(11), 샘플 벨브(12), 가스크로마토그래피(13), 기준컬럼(14), 분석컬럼(Carboxen 1004)(15)의 분석부로 구성되어 있다.The process apparatus of the present invention comprises a He gas (1), dimethyl ether (DME) (2), H2 O (3), mass flow rate regulator (4), the supply portion of the liquid pump (5); Reaction and separation of the
먼저, 분리막이 장착된 반응기에 촉매를 채우고 반응물인 디메틸에테르(DME)를 공급한다.First, a catalyst is charged to a reactor equipped with a separator and dimethyl ether (DME), which is a reactant, is supplied.
분리막 반응기에 사용되는 분리막은 수소를 선택 분리막으로 특별히 한정하지는 않으나, 특히, 팔라듐 합금막 또는 실리카막을 사용하는 경우에는 200 ∼ 500 ℃의 온도 범위에서 현저한 효과를 나타내어 보다 유리하다. 상기 분리막의 성능은 수소 투과도가 10-2 ㎤/㎠·㎝Hg·s ∼ 10-5 ㎤/㎠·㎝Hg·s이고, 수소 선택도가 100 ∼ 10000인 것을 선택 사용하는 것이 바람직하다. 수소 투과도가 10-5 ㎤/㎠·㎝Hg·s 미만이면 수소기체가 투과되는 속도가 느려 전환율 등의 저하우려가 있고 수소 선택도가 100 미만이면 수소 기체 이외의 일산화탄소와 같은 부생성물이 함께 투과되어 수소 순도가 높은 생성물을 얻기 힘들어짐으로써 높은 순도의 생성물이 필요한 연료전지 등에 적용시킬 경우 별도의 분리공정이 도입되어야 하는 문제가 있다.The separator used in the separator reactor is not particularly limited to hydrogen as a selective separator, but in particular, in the case of using a palladium alloy membrane or a silica membrane, the separator exhibits a remarkable effect in the temperature range of 200 to 500 ° C., which is more advantageous. The performance of the separator is preferably selected from those having a hydrogen permeability of 10−2
분리막은 기존의 디메틸에테르(DME)로부터 수소를 제조하는 반응기에 상기와 같은 조건을 만족하는 분리막이 장착된 반응기를 적용할 수 있으며, 상기 반응기를 적용하면 수소를 선택적으로 제거함으로써 반응조건인 온도와 압력이 보다 완화된 조건에서도 전환율 향상과 부반응물 억제에 의한 높은 효율을 얻을 수 있다. 기존의 분리막이 장착되지 않은 반응기에 비하여 본 발명의 분리막 반응기는 같은 조건에서 보다 반응전환율을 높이며 순수한 수소를 얻을 수 있다는 장점을 가지고 있다.Separation membrane can be applied to a reactor equipped with a membrane that satisfies the above conditions in the reactor for producing hydrogen from the existing dimethyl ether (DME), and when the reactor is applied to the reaction conditions by selectively removing hydrogen Even under conditions where the pressure is more relaxed, high efficiency can be obtained by improving conversion and suppressing side reactants. Compared to the conventional reactor without a separator, the separator reactor of the present invention has the advantage of increasing the reaction conversion rate and obtaining pure hydrogen under the same conditions.
또한, 본 발명은 촉매 존재하에 디메틸에테르(DME)의 수증기 개질 반응으로 생성물인 수소와 부생성물인 일산화탄소, 이산화탄소, 메탄 및 미반응된 DME의 혼합물로부터 목적생성물인 수소를 선택적으로 제거하고, 디메틸에테르(DME)의 전환율을 향상시키면서 부생성물인 일산화탄소를 억제시키는데 큰 특징이 있다. 기존의 촉매만을 사용하는 경우에는 반응 평형에 의해 수소와 일산화탄소가 양론비적으로 형성되었으나, 본 발명의 분리막 반응기를 사용하는 경우에는 수소에 대한 선택적 투과성 막을 사용함으로써 생성물인 수소를 선택적으로 분리 제거하므로 평형이상으로 디메틸에테르(DME)의 전환율을 향상시키고 부생성물인 일산화탄소 등의 투과를 억제시킴과 동시에 특히 수성가스 반응에 효과적인 Zn 조촉매의 첨가로 일산화탄소 등의 생성을 억제시켜 주는 효과를 가짐으로써 생성되는 수소의 순도를 향상시킨다.In addition, the present invention selectively removes the target product hydrogen from the mixture of the product hydrogen and by-products carbon monoxide, carbon dioxide, methane and unreacted DME by the steam reforming reaction of dimethyl ether (DME) in the presence of a catalyst, dimethyl ether It has a great feature in suppressing byproduct carbon monoxide while improving the conversion rate of (DME). In the case of using only the conventional catalyst, hydrogen and carbon monoxide were formed in a stoichiometric ratio by the reaction equilibrium, but in the case of using the membrane reactor of the present invention, an optional permeable membrane for hydrogen is used to selectively remove and remove the hydrogen as a product. In this way, it is possible to improve the conversion rate of dimethyl ether (DME) and to suppress the permeation of carbon monoxide, a byproduct, and to suppress the production of carbon monoxide by adding Zn cocatalyst, which is particularly effective for water gas reaction. Improves the purity of hydrogen.
상기 촉매는 종래 당 분야에서 사용되는 알칼리 금속-부재 촉매 조성물을 사용할수 있으며, 본 발명에서는 Cu/Zn/Al2O3계 촉매를 사용하는 것이 좋다. 본 발명에서는 상기 촉매를 함침법으로 제조하여 60 ∼ 80 메시 크기만을 선별하여 반응에 사용한다.The catalyst may use an alkali metal-free catalyst composition conventionally used in the art, and in the present invention, it is preferable to use a Cu / Zn / Al2 O3 based catalyst. In the present invention, the catalyst is prepared by the impregnation method, and only 60 to 80 mesh sizes are used for the reaction.
이와 같이, 본 발명의 막반응기를 이용하게 되면 반응이 종결된 후에 별도의 분리 공정을 거치지 않으므로 에너지 소비를 절감시킬 수 있다. 더욱이 생성물을 선택적으로 제거함으로써 평형 전환율 및 순도를 개선에 효과적이며, 반응과 분 리 공정을 동시에 수행함으로서 경제적으로 생산성을 향상시키는데 효과적으로 이용될 수 있다.As such, when the membrane reactor of the present invention is used, energy consumption may be reduced since the reaction is not completed, and thus, a separate separation process is not performed. Furthermore, by selectively removing the product, it is effective to improve the equilibrium conversion and purity, and can be effectively used to improve productivity economically by carrying out the reaction and separation process simultaneously.
이상에서 설명한 바와 같은 본 발명은 다음의 실시예에 의거하여 더욱 상세하게 설명하겠는 바, 본 발명이 이에 한정되는 것은 아니다.The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited thereto.
실시예 1Example 1
Cu(NO3)2·2.5H2O 화합물과 Zn(NO3)2·6H2O 화합물을 각각 증류수에 충분히 녹인 후, 담체인 Al2O3을 넣고 교반하여 담지시켰다. 그 후에 열을 가하면서 서서히 증류수를 건조시키고, 상기 증류수를 완전하게 제거하기 위하여 120 ??의 건조기에서 24시간 동안 건조한 후, 공기를 30 mL/min의 유속으로 흘려주면서 400 ??에서 2시간 동안 소성하여 5 중량% Cu/1 중량% Zn/Al2O3 촉매를 얻었다. 상기 얻어진 촉매를 60 ∼ 80 mesh의 크기만을 선별하여 반응에 사용하였다.After the Cu (NO3 )2 .2.5H2 O compound and the Zn (NO3 )2 .6H2 O compound were dissolved in distilled water, respectively, Al2 O3 serving as a carrier was added thereto, followed by stirring. Then, distilled water was slowly dried while applying heat, dried for 24 hours in a dryer at 120 ° C. to completely remove the distilled water, and then air was flowed at a flow rate of 30 mL / min for 2 hours at 400 ° C. Firing gave 5 wt% Cu / 1 wt% Zn / Al2 O3 catalyst. The obtained catalyst was used for the reaction by selecting only 60 to 80 mesh in size.
다음 도 1에 나타낸 분리분리막 반응기와 상기에서 제조된 촉매를 이용하여 하기의 공정으로 디메틸에테르로부터 수소를 제조하였다.Next, hydrogen was prepared from dimethyl ether by the following process using the separator membrane reactor shown in FIG. 1 and the catalyst prepared above.
가스크로마토그래피(13)의 운반가스인 He(1), DME(2) 및 물(3)을 분리막 반응기(9)에 공급하였다. 이때, DME(2)는 질량 유속 조절기(4)를 통하여 공간속도 10㎖/min 정도로 일정하게 유지시키고, 수증기 개질의 매개체인 물(3)은 액체 펌프(5)를 통하여 반응기에 공급되며, 분리막 반응기(9) 공급되기 전에 물(3)을 수증기 상태로 만들기 위하여 액체 펌프(5)와 분리막 반응기(9) 사이에 열선을 사용 하여 130 ℃의 온도로 미리 가열하여 수증기로 만든 후 공급하였다. 공급되는 DME(2)와 물(3)의 비율은 1 : 5로 유지하였다.He (1), DME (2) and water (3), which are carrier gases of the gas chromatography (13), were supplied to the membrane reactor (9). At this time, the DME (2) is maintained at a constant space velocity of about 10ml / min through the mass flow rate regulator (4), water (3), a medium for steam reforming is supplied to the reactor through the liquid pump (5), the separation membrane In order to make the water (3) into a water vapor state before the reactor (9) is supplied, it was heated to a temperature of 130 ° C. using a hot wire between the liquid pump (5) and the membrane reactor (9), and then supplied with steam. The ratio of DME (2) to water (3) supplied was maintained at 1: 5.
분리막 반응기(9)는 5 중량% Cu/1 중량% Zn/Al2O3계 촉매(60 ∼ 80 mesh의 크기) 2 g을 팔라듐막 위에 충진한 후 반응물을 흘려주고, 연소로(9)를 이용하여 400 ℃의 반응온도를 올려주었다. 분리막 반응기(9) 내부의 온도는 열전대 온도계(7)을 사용하여 측정하며 온도조절기(6)을 통하여 반응기의 온도를 조절하였다. 미반응된 물은 냉각조(10)를 사용하여 제거하며, 완벽한 물의 제거를 위하여 습도 트랩(11)을 사용하였다.The membrane reactor (9) was charged with 2 g of 5 wt% Cu / 1 wt% Zn / Al2 O3 based catalyst (size of 60 to 80 mesh) on the palladium membrane to flow the reactants, and the combustion furnace (9) The reaction temperature of 400 ℃ was raised. The temperature inside the membrane reactor (9) was measured using a thermocouple thermometer (7) and the temperature of the reactor was controlled through the temperature controller (6). Unreacted water was removed using a
상기 반응 후 얻어진 미반응물과 생성물을 분석하기 위해 가스크로마토그래피(13)를 이용하고, 분석시 분석컬럼(15)은 carboxen 1004를 사용하여 얻어진 미반응물과 생성물을 샘플벨브(12)로부터 일정량을 주입하여 정량 ·정성 분석을 하였다. 얻어진 생성물인 수소, 일산화탄소, 이산화탄소, 메탄은 가스크로마토그래피(13)에 표시되는 각 기체의 면적으로부터 각각의 몰수를 얻기 위한 각 기체별 부피에 대한 면적의 그래프를 통하여 얻어진 자료를 이용하였다. 분석시 실제 유출되는 유속을 측정한 후 각 기체의 몰분율을 구하여 각 기체별 몰분율과 실제 유속을 곱하여 실제 유출되는 각 기체의 유속을 구하였다.Gas chromatography (13) is used to analyze unreacted products and products obtained after the reaction, and analysis column (15) injects a predetermined amount of unreacted products and products obtained by using carboxen 1004 from the sample valve (12). And quantitative and qualitative analysis. The obtained products, hydrogen, carbon monoxide, carbon dioxide, and methane, were used as data obtained through a graph of the area of each gas volume to obtain the number of moles of each gas from the area of each gas shown in the gas chromatography (13). After measuring the actual flow rate during the analysis, the mole fraction of each gas was calculated and multiplied by the mole fraction of each gas and the actual flow rate to obtain the flow rate of each gas.
실시예 2 ∼ 3Examples 2 to 3
상기 실시예 1과 동일하게 실시하되, 촉매의 종류를 달리하여 반응을 수행하 고, 반응기로부터 얻은 결과를 다음 표 1에 나타내었다.In the same manner as in Example 1, the reaction was carried out by varying the type of catalyst, and the results obtained from the reactor are shown in Table 1 below.
비교예 1 ∼ 3Comparative Examples 1 to 3
상기 실시예 1과 동일하게 실시하되, 분리막 반응기 대신에 고정층 반응기를 사용하고 촉매의 종류도 달리하여 반응을 수행하였으며, 반응기로부터 얻은 결과를 다음 표 1에 나타내었다.The reaction was carried out in the same manner as in Example 1, but using a fixed bed reactor instead of a membrane reactor and different kinds of catalysts, and the results obtained from the reactor are shown in Table 1 below.
상기 표 1에 나타낸 바와 같이, 본 발명에 따라 분리막 반응기를 사용한 실시예 1 ∼ 3이 고정층 반응기를 사용한 비교예 1 ∼ 3에 비해 DME 전환율이 증가하였으며, 일산화탄소의 생성억제의 효과도 우수함을 알 수 있었다. 또한, Cu/Al2O3촉매에 조촉매로 Zn을 첨가 사용으로 CO의 생성을 억제에도 효과가 있음을 확인할 수 있었다.As shown in Table 1, Examples 1 to 3 using the membrane reactor according to the present invention increased the DME conversion rate compared to Comparative Examples 1 to 3 using the fixed bed reactor, it can be seen that the effect of inhibiting the production of carbon monoxide is also excellent. there was. In addition, it was confirmed that addition of Zn as a cocatalyst to the Cu / Al2 O3 catalyst was also effective in suppressing the generation of CO.
상기에서 살펴본 바와 같이, DME로부터 수소를 제조하는 공정에서 DME의수증기 개질 반응과 생성된 수소의 분리를 동시에 수행할 수 있는 분리막을 도입하여, 생성물인 수소와 일산화탄소, 이산화탄소, 메탄, 미반응 DME을 각각 분리할 수 있어, 반응 후, 별도의 공정이 생략되어 경제적인 효과가 크며, 또한 선택적으로 수소를 분리해 줌으로써 DME 전환율 상승을 이끌어 낼 수 있으므로 소형 개질기로서 우수한 성능을 가진다고 판단 할 수 있다. As described above, in the process for producing hydrogen from the DME, a separator capable of simultaneously performing the steam reforming reaction of the DME and separation of the generated hydrogen was introduced to produce hydrogen, carbon monoxide, carbon dioxide, methane, and unreacted DME as products. Since it can be separated from each other, a separate process is omitted after the reaction, so the economic effect is large, and by selectively separating hydrogen, it is possible to induce an increase in DME conversion rate, and thus it can be judged to have excellent performance as a small reformer.
Claims (4)
Translated fromKoreanPriority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040056403AKR20060007574A (en) | 2004-07-20 | 2004-07-20 | Hydrogen Production Method Using Membrane Reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040056403AKR20060007574A (en) | 2004-07-20 | 2004-07-20 | Hydrogen Production Method Using Membrane Reactor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20060007574Atrue KR20060007574A (en) | 2006-01-26 |
Family
ID=37118806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020040056403ACeasedKR20060007574A (en) | 2004-07-20 | 2004-07-20 | Hydrogen Production Method Using Membrane Reactor |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20060007574A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100795883B1 (en)* | 2006-06-26 | 2008-01-21 | (주)에어레인 | Fuel reforming method using hydrogen separation membrane and fuel reforming device using same |
| KR100816879B1 (en)* | 2006-11-29 | 2008-03-26 | 한국화학연구원 | Membrane reactor carried out during the steam reforming and carbon monoxide removal of hydrocarbons and hydrogen production method using the same |
| US8597383B2 (en) | 2011-04-11 | 2013-12-03 | Saudi Arabian Oil Company | Metal supported silica based catalytic membrane reactor assembly |
| US8663566B2 (en) | 2010-05-19 | 2014-03-04 | Korea Institute Of Energy Research | Fluidized bed water gas shift membrane for simultaneous CO2 separation and CO2 separation method using the same |
| US9745191B2 (en) | 2011-04-11 | 2017-08-29 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
| KR20230132644A (en)* | 2022-03-08 | 2023-09-18 | (주)바이오프랜즈 | Dme reforming system for smart farming and power plant |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990068056A (en)* | 1998-01-21 | 1999-08-25 | 지롤라 죠지오 | PROCESS FOR PREPARATlON OF HYDROGEN-RICH GAS |
| KR20010110412A (en)* | 1999-01-11 | 2001-12-13 | 추후제출 | Reclaiming of purge gas from hydrotreaters and hydrocrackers |
| KR20020024586A (en)* | 1999-05-14 | 2002-03-30 | 추후제출 | Hydrogen recycle and acid gas removal using a membrane |
| JP2003192302A (en)* | 2001-12-26 | 2003-07-09 | Sumitomo Seika Chem Co Ltd | Hydrogen production apparatus |
| KR20040017491A (en)* | 2002-08-21 | 2004-02-27 | 에스케이 주식회사 | Method for preparing synthesis gas from dimethyl ether |
- 2004
- 2004-07-20KRKR1020040056403Apatent/KR20060007574A/ennot_activeCeased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990068056A (en)* | 1998-01-21 | 1999-08-25 | 지롤라 죠지오 | PROCESS FOR PREPARATlON OF HYDROGEN-RICH GAS |
| KR20010110412A (en)* | 1999-01-11 | 2001-12-13 | 추후제출 | Reclaiming of purge gas from hydrotreaters and hydrocrackers |
| KR20020024586A (en)* | 1999-05-14 | 2002-03-30 | 추후제출 | Hydrogen recycle and acid gas removal using a membrane |
| JP2003192302A (en)* | 2001-12-26 | 2003-07-09 | Sumitomo Seika Chem Co Ltd | Hydrogen production apparatus |
| KR20040017491A (en)* | 2002-08-21 | 2004-02-27 | 에스케이 주식회사 | Method for preparing synthesis gas from dimethyl ether |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100795883B1 (en)* | 2006-06-26 | 2008-01-21 | (주)에어레인 | Fuel reforming method using hydrogen separation membrane and fuel reforming device using same |
| KR100816879B1 (en)* | 2006-11-29 | 2008-03-26 | 한국화학연구원 | Membrane reactor carried out during the steam reforming and carbon monoxide removal of hydrocarbons and hydrogen production method using the same |
| US8663566B2 (en) | 2010-05-19 | 2014-03-04 | Korea Institute Of Energy Research | Fluidized bed water gas shift membrane for simultaneous CO2 separation and CO2 separation method using the same |
| US8597383B2 (en) | 2011-04-11 | 2013-12-03 | Saudi Arabian Oil Company | Metal supported silica based catalytic membrane reactor assembly |
| US9745191B2 (en) | 2011-04-11 | 2017-08-29 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
| US10071909B2 (en) | 2011-04-11 | 2018-09-11 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
| US10093542B2 (en) | 2011-04-11 | 2018-10-09 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
| US10252911B2 (en) | 2011-04-11 | 2019-04-09 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic systems |
| US10252910B2 (en) | 2011-04-11 | 2019-04-09 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
| KR20230132644A (en)* | 2022-03-08 | 2023-09-18 | (주)바이오프랜즈 | Dme reforming system for smart farming and power plant |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11292717B2 (en) | Method for producing methanol from synthesis gas without the emission of carbon dioxide | |
| Stucki et al. | Coupled CO2 recovery from the atmosphere and water electrolysis: Feasibility of a new process for hydrogen storage | |
| EP2167706B1 (en) | Electrolysis of carbon dioxide in aqueous media to carbon monoxide and hydrogen for production of methanol | |
| US8138380B2 (en) | Electrolysis of carbon dioxide in aqueous media to carbon monoxide and hydrogen for production of methanol | |
| KR101495085B1 (en) | Efficient selective conversion of carbon dioxide to methanol, dimethyl ether and derived products | |
| KR101579051B1 (en) | Method for converting carbon dioxide to dimethyl ether using double reforming of methane or natural gas | |
| Alent’ev et al. | Membrane technologies for decarbonization | |
| AU2010234500B2 (en) | Rendering coal as an environmentally carbon dioxide neutral fuel and a regenerative carbon source | |
| US8461218B2 (en) | Rendering petroleum oil as an environmentally carbon dioxide neutral source material for fuels, derived products and as a regenerative carbon source | |
| CA2186222A1 (en) | Diaphragm reactor for converting gaseous base materials | |
| US20230219816A1 (en) | Method of the production of hydrogen | |
| KR20060007574A (en) | Hydrogen Production Method Using Membrane Reactor | |
| EP1230203B1 (en) | Cogeneration of methanol and electrical power | |
| US12139450B2 (en) | CO2 conversion device | |
| KR20210002983A (en) | Dimethyl ether synthesis process exploiting steel-work off-gases | |
| JPWO2004076063A1 (en) | Catalyst for producing liquefied petroleum gas, method for producing the same, and method for producing liquefied petroleum gas using the catalyst | |
| EA012595B1 (en) | A method of converting natural gas into fuels | |
| Cholewa et al. | Process Intensification Strategies for Power-to-X Technologies. ChemEngineering 2022, 6, 13 | |
| RU2803569C1 (en) | Method for hydrogen production | |
| US12060325B2 (en) | Methods of producing dimethyl carbonate | |
| KR102176909B1 (en) | Methanol synthesis process exploiting by-product gas from steelmaking plant | |
| Mirimousavi | Simulation of methanol production from biogas through carbon dioxide capture method | |
| RU2175961C2 (en) | Liquid fuel production process | |
| EP4570742A1 (en) | Method for producing hydrogen | |
| CN119768386A (en) | Process for producing dimethyl ether and hydrogen from methane using solid metal oxide reactants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| PA0109 | Patent application | Patent event code:PA01091R01D Comment text:Patent Application Patent event date:20040720 | |
| PA0201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| PE0902 | Notice of grounds for rejection | Comment text:Notification of reason for refusal Patent event date:20060113 Patent event code:PE09021S01D | |
| PG1501 | Laying open of application | ||
| E601 | Decision to refuse application | ||
| PE0601 | Decision on rejection of patent | Patent event date:20060511 Comment text:Decision to Refuse Application Patent event code:PE06012S01D Patent event date:20060113 Comment text:Notification of reason for refusal Patent event code:PE06011S01I |