KR100314829B1 - Methanol reforming apparatus for fabricating highly purified hydrogen - Google Patents

Methanol reforming apparatus for fabricating highly purified hydrogen Download PDF

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KR100314829B1
KR100314829B1 KR1019950006785A KR19950006785A KR100314829B1 KR 100314829 B1 KR100314829 B1 KR 100314829B1 KR 1019950006785 A KR1019950006785 A KR 1019950006785A KR 19950006785 A KR19950006785 A KR 19950006785A KR 100314829 B1 KR100314829 B1 KR 100314829B1
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reforming
combustion
pipe
supply pipe
combustion catalyst
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KR960034070A (en
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정현종
김선
한재성
정성재
정연관
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유승렬
에스케이 주식회사
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    • 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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1023—Catalysts in the form of a monolith or honeycomb

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
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  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

PURPOSE: Provided is a methanol reforming apparatus for fabricating highly purified hydrogen, wherein the apparatus includes a pressure swing adsorption device to highly purify hydrogen. CONSTITUTION: The apparatus(1) comprises an outer housing, a reforming tube(9) defined by coaxially arranged inner and outer cylinders, a reforming catalyst(10) filled in the reforming tube(9) between the inner cylinder and the outer cylinder, a plurality of combustion catalyst layers(2) separately installed inside the inner cylinder of the reforming tube(9) in parallel with each other in horizontal direction, a porous fuel supply pipe(3) installed at the center of the inner cylinder of the reforming tube(9) to penetrate the combustion catalyst layers(2), and a helical fuel vaporizing coil(4) surrounding the fuel supply pipe(4).

Description

고순도 수소 제조를 위한 메탄올 개질장치Methanol Reformer for High Purity Hydrogen Production

본 발명은 메탄올을 물과 혼합하여 개질촉매상에서 수소 및 일산화탄소, 이산화탄소 등을 생산한 뒤, PSA(pressure swing adsorptin)장치를 통하여 고순도 수소를 분리, 생산하기 위한 메탄올개질장치에 관한 것으로서, 더욱 상세하게는 메탄올 개질장치 내부에 다수의 연소촉매층 및 연소실내의 온도를 가능한 낮게 유지하고 개질촉매층의 최적의 온도분포를 구현하여 열효율을 향상시키고, 또한 연소촉매층 사이에 연료기화코일을 구비하여 개질장치의 단순화 및 소형화를 이룰 수 있도록 한 것에 관한 것이다.The present invention relates to a methanol reformer for separating and producing high purity hydrogen through a pressure swing adsorptin (PSA) apparatus after producing methanol, water, hydrogen and carbon monoxide, carbon dioxide, etc. in a reforming catalyst. Improves thermal efficiency by keeping the temperature of the plurality of combustion catalyst layers and the combustion chamber as low as possible in the methanol reformer and by implementing the optimum temperature distribution of the reforming catalyst layer. Also, the fuel vaporization coil is provided between the combustion catalyst layers to simplify the reforming apparatus. And to enable miniaturization.

일반적으로 메탄올 개질장치는 수소생산장치 및 연료전지시스템에 포함되어 전체시스템의 고효율화, 단순화, 소형화 등을 목표로 개발되어 왔다.In general, a methanol reformer is included in a hydrogen production apparatus and a fuel cell system, and has been developed for the purpose of high efficiency, simplification, and miniaturization of the entire system.

특히 수소생산장치의 경우 수소를 생산하기 위한 방법으로 촉매개질방식 및 전기분해방식이 있는데 촉매개질방식이 전기분해방식에 비하여 사용전력량이 작다는 장점으로 인하여 비교적 큰 용량의 수소생산장치에 주로 채택되고 있다.In particular, in the case of a hydrogen production apparatus, there are a catalyst reforming method and an electrolysis method for producing hydrogen. The catalyst reforming method is mainly adopted in a relatively large capacity hydrogen production apparatus due to the advantage of using less power than the electrolysis method. have.

상기와 같은 메탄올 개질장치에 있어서 일어나는 반응은 다음과 같다.The reaction occurring in the methanol reformer as described above is as follows.

(1) CH3OH = CO + 2H2 (1) CH 3 OH = CO + 2H 2

(2) CO + H2O = CO2+ H2 (2) CO + H 2 O = CO 2 + H 2

(3) CH3OH + H2O = CO2+ 3H2 (3) CH 3 OH + H 2 O = CO 2 + 3H 2

(4) CO + 3H2= CH4+ H2O(4) CO + 3H 2 = CH 4 + H 2 O

메탄올의 수증기개질반응은 식(1)과 식(2)로써 표시되며, 이 반응은 전체적으로 식(3)과 같이 표시된다. 식(3)의 메탄올 수증기개질반응은 흡열반응이므로 메탄올의 전환율을 높이기 위해서는 외부로부터의 반응열 공급 및 개질촉매상에서의 최적의 운전조건 유지가 필요하다.The steam reforming reaction of methanol is represented by equations (1) and (2), and the reaction is expressed in general as shown in equation (3). Since the methanol steam reforming reaction of the formula (3) is an endothermic reaction, it is necessary to supply reaction heat from the outside and maintain optimum operating conditions on the reforming catalyst in order to increase the conversion of methanol.

한편 식(1)과 식(2)에 의하여 생성된 일산화탄소와 수소가 식(4)와 같이 반응하여 메탄 및 물이 발생되는 메탄화(Methanation)반응이 일어날 수 있는데 이 반응은 수소의 수율을 감소시키는 결과가 되므로 적절한 운전조건 및 촉매선정, 원료인 메탄올과 물의 공급비의 조절을 통하여 식(4)와 같은 메탄화반응이 가급적 일어나지 않도록 하여야 한다.On the other hand, carbon monoxide and hydrogen produced by the formulas (1) and (2) react as shown in the formula (4), and methanation reaction occurs, where methane and water are generated, which reduces the yield of hydrogen. As a result, the methanation reaction as shown in Equation (4) should be avoided through proper operation conditions, catalyst selection, and control of the feed ratio of methanol and water as raw materials.

종래의 메탄올개질장치(일본, 공개특허 제 91-218902)는 제 1도에 개락적으로 나타난 바와 같이 개질장치(31)내에 연소실(32)이 형성되어 있으며 연소실(32)주위로 열교환실(36)이 형성되어 있다. 열교환실(36)내부 및 연소실(32)내부에는 원료가열관(37)(37')이 설치되어 있으며 연소실(32)의 경우 원료가열관(37)주위로 연소촉매(33)가 충진되어 있다. 한편 원료가열관(37)은 개질가스생성관(38)과 연결되어 있으며 개질가스생성관(38)주위에도 연소촉매(33)가 충진되어 있다.In the conventional methanol reformer (Japanese Patent Laid-Open No. 91-218902), as shown in FIG. 1, a combustion chamber 32 is formed in the reformer 31, and a heat exchange chamber 36 is disposed around the combustion chamber 32. ) Is formed. In the heat exchange chamber 36 and the combustion chamber 32, raw material heating tubes 37 and 37 ′ are provided. In the combustion chamber 32, a combustion catalyst 33 is filled around the raw material heating tube 37. . Meanwhile, the raw material heating tube 37 is connected to the reformed gas generating tube 38, and the combustion catalyst 33 is filled around the reformed gas generating tube 38.

상기와 같이 구성된 종래의 개질장치에서는 개질장치(31)의 상단에 설치된 연료공급관(35) 및 연료노즐(34)을 통하여 연소용 메탄올과 공기의 혼합물이 유입되어 연소촉매(33)상에서 연소하게 된다. 이때 연소실(32)내의 연료가열관(37) 및 개질가스생성관(38)을 가열한 뒤 열교환실로 유입되어 연소실(32)주위의 연료가열관(37')을 추가로 가열한 뒤 연소가스출구(39)로 배출되게 된다.In the conventional reformer configured as described above, a mixture of methanol and air for combustion is introduced through the fuel supply pipe 35 and the fuel nozzle 34 installed on the top of the reformer 31 to combust on the combustion catalyst 33. . At this time, the fuel heating tube 37 and the reformed gas generating tube 38 in the combustion chamber 32 are heated, and then flowed into the heat exchange chamber to further heat the fuel heating tube 37 'around the combustion chamber 32, and then the combustion gas outlet. Discharged to (39).

한편, 원료인 메탄올과 물의 혼합물은 개질장치(31)의 상단 우측에 설치된 수소원료공급관(40)을 통하여 유입되며 원료가열관(37)(37')을 통과하면서 기화된 후 개질가스생성관(38)으로 유입되게 된다. 유입된 수소원료는 개질촉매(41)(41')상에서 개질가스로 전환되어 개질가스출구(42)로 배출된다.Meanwhile, the mixture of methanol and water, which is a raw material, is introduced through the hydrogen raw material supply pipe 40 installed at the upper right side of the reforming unit 31 and vaporized while passing through the raw material heating tubes 37 and 37 '. 38). The introduced hydrogen raw material is converted into reformed gas on the reforming catalysts 41 and 41 'and discharged to the reformed gas outlet 42.

상기와 같은 종래의 메탄올개질장치는 연소용 공기와 연료가 개질장치 외부에서 혼합되어 연료공급관(35)으로 유입되므로 초기에 연소반응이 활발하게 진행되어 연소촉매층의 입구온도가 매우 높게 되므로(1000℃이상)연소촉매 및 개질장치의온도 내구성이 높아야 한다. 또한 연소촉매층이 구형의 연소촉매로 층진되어 있으므로 연소열은 주로 전도에 의한 열전달에 의존할 수 밖에 없으므로 원활한 수소원료의 기화를 위하여 연소실(32) 내부가 400 - 1200℃의 비교적 고온으로 유지되어야 한다. 또한 연소실 내부가 고온이므로 개질촉매(41)의 운전조건이 200 - 500℃가 되어 온도내구성이 높은 촉매선정이 불가피한 것이다.In the conventional methanol reformer as described above, since combustion air and fuel are mixed outside the reformer and introduced into the fuel supply pipe 35, the combustion reaction is actively progressed at an initial stage, and thus the inlet temperature of the combustion catalyst layer becomes very high (1000 ° C.). The durability of combustion catalyst and reformer should be high. In addition, since the combustion catalyst layer is layered with a spherical combustion catalyst, the heat of combustion is inevitably dependent on heat transfer by conduction, so the inside of the combustion chamber 32 must be maintained at a relatively high temperature of 400-1200 ° C for the vaporization of the hydrogen raw material. In addition, since the inside of the combustion chamber is a high temperature, the operating conditions of the reforming catalyst 41 is 200-500 ° C., so that the selection of a catalyst having high temperature durability is inevitable.

본 발명은 상기와 같은 종래기술의 문제점을 감안하여 안출한 것으로 본 발명의 목적은 개질장치의 운전온도범위를 가능한 낮추어 열효율을 향상시키고 연소실내에서 최적의 연소조건 및 온도분포를 구현하여 원하는 메탄올의 전환율 및 개질가스의 조성을 얻도록 하는 개질장치를 제공하는 것이다.The present invention has been made in view of the problems of the prior art as described above. The object of the present invention is to reduce the operating temperature range of the reforming unit as much as possible to improve the thermal efficiency and to realize the optimum combustion conditions and temperature distribution in the combustion chamber of the desired methanol. It is to provide a reforming apparatus to obtain the conversion rate and the composition of the reformed gas.

상기와 같은 목적을 달성하기 위한 본 발명의 특징은 개질장치내에 수개의 연소촉매층이 일정간격을 두고 설치되고, 연소촉매층 중심으로 다공성 연료공급관이 설치되어 각 연소촉매층에서의 균일한 연소반응을 분할, 공급할 수 있도록하여 각 연소촉매층에서의 균일한 연소반응을 유도하고 연소촉매층사이 공간에 원료기화코일을 구비하여 원료기 운전조건에 맞게 기화되어 개질촉매층으로 공급되도록 형성된 것이다.A characteristic of the present invention for achieving the above object is that several combustion catalyst layers are installed in a reformer at regular intervals, and a porous fuel supply pipe is installed around the combustion catalyst layer to divide a uniform combustion reaction in each combustion catalyst layer. It can be supplied to induce a uniform combustion reaction in each combustion catalyst layer, and the raw material vaporization coil is provided in the space between the combustion catalyst layer is formed to be vaporized in accordance with the operating conditions of the raw material machine to be supplied to the reforming catalyst layer.

이하, 본 발명에 의한 메탄올개질장치를 첨부도면을 참조하여 구체적으로 설명하면 다음과 같다.Hereinafter, the methanol reformer according to the present invention will be described in detail with reference to the accompanying drawings.

제 2도는 본 발명에 의한 메탄올개질장치의 개략적인 정단면도로서, 개질장치 (1) 내부에 이중관 형태의 개질관(9)이 설치되고 개질관의 내부에는 개질촉매 (10)가 충진되어 있는 개질장치에 있어서 상기 개질관 (9)의 내측 공간에 다수의연소촉매층(2)이 일정한 간격을 두고 상하로 설치되어 있고, 상기 연소촉매층(2) 중심부에 연료분사공(13) 다수 천공된 연료공급관 (3)이 관통되어 설치되어 있으며, 상기 연소촉매층 (2) 사이에 원료기화코일(4)이 연료공급관(3)의 주위로 설치되어 상기 개질관(9)에 연결되어 있으며, 개질장치 하부에 개질관(9)을 지지하기 위한 지지대(12)가 설치되어 있다.2 is a schematic sectional view of the methanol reformer according to the present invention, in which a reformer (9) in the form of a double tube is installed inside the reformer (1), and a reforming catalyst (10) is filled in the reformer. In the apparatus, a plurality of combustion catalyst layers (2) are installed vertically at regular intervals in the inner space of the reforming pipe (9), and a plurality of fuel injection holes (13) perforated in the center of the combustion catalyst layer (2). (3) is penetrated, and the raw material vaporization coil (4) is installed around the fuel supply pipe (3) between the combustion catalyst layer (2) and connected to the reforming pipe (9), A support 12 for supporting the reformed pipe 9 is provided.

상기 연소촉매층(2)은 하니컴구조의 기공을 가진 원통형의 세라믹 지지체(미국, Corning사 제품)에 백금(Pt)에 팔라듐(Pd)등을 담지하여 제조한 것으로서 연료공급관(3) 및 연료기화코일(4)이 통과할 수 있도록 일정한 크기의 통로를 가공한 형태의 것이다.The combustion catalyst layer (2) is manufactured by supporting palladium (Pd) in platinum (Pt) on a cylindrical ceramic support having a honeycomb structure pores (manufactured by Corning, USA), and supplying a fuel supply pipe (3) and a fuel vaporization coil. It is of the form that a certain size passage is processed so that (4) can pass.

그리고, 상기 연료공급관(3)에 형성된 연료분사공(13)은 하부에서 상부로 점차적으로 많거나 크게 형성시켜 연료분사공(13)을 통해 분사되는 연료량이 상,하가 고르게 분사되도록 하며, 상기 연료공급관(3)의 하부에는 연료공급입구관(11)를 연결시켜 연료가 공급되도록 하고, 상기 개질장치(1)의 하부에 공기공급관(6)를 형성시켜 개질장치(1)내부로 공기가 유입되도록 하며, 상기 원료기화코일(4)의 하부에 원료공급관(7)을 연결시켜 원료가 공급되도록 하되, 상기 원료기화코일(4)은 개질관(9)에 연결시켜 기화된 원료가 개질관의 내부로 유입되도록 한다. 또한, 상기 개질장치(1)의 외측 하부에는 연소가스출구(5)를 설치하며, 개질관(9)의 하부에는 개질가스출구(8)를 형성시킨다.In addition, the fuel injection hole 13 formed in the fuel supply pipe 3 is gradually formed from the lower portion to the upper portion or larger so that the amount of fuel injected through the fuel injection hole 13 is injected evenly up and down, A fuel supply inlet pipe 11 is connected to the lower part of the fuel supply pipe 3 to supply fuel, and an air supply pipe 6 is formed at the lower part of the reformer 1 to supply air into the reformer 1. The raw material vaporization coil 4 is connected to the lower part of the raw material vaporization coil 4 to supply raw materials, but the raw material vaporization coil 4 is connected to the reforming pipe 9 so that the vaporized raw material is reformed. To get inside the. In addition, a combustion gas outlet 5 is provided in the lower part of the outer side of the reformer 1, and a reformed gas outlet 8 is formed in the lower part of the reforming pipe 9.

상기와 같은 본 발명에 의한 메탄올개질장치의 작용 및 효과를 설명하면, 개질장치의 하부에 설치된 공기입구(6)를 통하여 연소용 공기가 유입되고 연소용 연료는 개질장치 하부의 연료입구(11)로 부터 유입된 뒤 다공성 연료공급관(3)을 통하여 각 연소촉매층(2) 사이 공간으로 분할 공급되면서, 각 연소촉매층(2)에서는 균일한 연소반응이 일어나게 되며, 연소열은 전도 및 대류효과에 의하여 개질관(9) 및 원료기화코일(4)에 필요한 열량을 공급하게 된다. 이때 연료공급관(3)에 천공된 연료분사공(13)이 하부에서 상부로 갈수록 점진적으로 많게 되어 있어 각 연소촉매층(2)으로 공급되는 연료량이 조절되므로 개질장치 하부에 위치한 연소촉매층에서는 완전연소를 유도하여 연소촉매층 및 개질관(9) 하부의 과열현상을 방지하고, 각 연소촉매층에서의 균일한 연소반응을 유도함으로써 연소실내에 최적의 온도분포를 유지할 수 있는 것이다.Referring to the operation and effect of the methanol reformer according to the present invention as described above, the combustion air is introduced through the air inlet 6 installed in the lower portion of the reformer and the fuel for combustion is the fuel inlet 11 of the lower reformer. After being supplied from the gas through the porous fuel supply pipe (3) and dividedly supplied to the space between each combustion catalyst layer (2), uniform combustion reaction occurs in each combustion catalyst layer (2), and the heat of combustion is reformed by conduction and convection effects. The amount of heat required for the tube 9 and the raw material vaporization coil 4 is supplied. At this time, since the fuel injection hole 13 drilled in the fuel supply pipe 3 gradually increases from the lower part to the upper part, the amount of fuel supplied to each combustion catalyst layer 2 is controlled, so that the combustion catalyst layer located at the bottom of the reforming device is completely burned. It is possible to maintain the optimum temperature distribution in the combustion chamber by inducing the combustion catalyst layer to prevent overheating of the lower part of the combustion catalyst layer and the reforming pipe 9 and inducing a uniform combustion reaction in each combustion catalyst layer.

그리고, 연소촉매층(2)을 통과한 연소가스는 개질관(9)의 외측 공간방향으로 유입되어 개질관에 연소열을 추가로 공급한 뒤 연소가스출구(5)를 통하여 배출되게 된다.Then, the combustion gas passing through the combustion catalyst layer 2 flows into the outer space direction of the reforming pipe 9 to further supply combustion heat to the reforming pipe and then is discharged through the combustion gas outlet 5.

한편, 원료인 메탄올과 물의 혼합물은 원료공급관(7)으로 유입되어 원료기화코일(4)을 통과하면서 연소열에 의하여 기화한 후 개질관(9)의 상부로 부터 개질촉매(10)층에 유입되는데 개질촉매(10)상에서 수소 및 이산화탄소, 일산화탄소, 메탄 등으로 전환되어 개질가스출구(8)로 배출된다.Meanwhile, a mixture of methanol and water, which is a raw material, flows into the raw material supply pipe 7 and passes through the raw material vaporization coil 4 and vaporizes with combustion heat, and then flows into the reforming catalyst 10 layer from the top of the reformed pipe 9. The reformed catalyst 10 is converted into hydrogen and carbon dioxide, carbon monoxide, methane, and discharged to the reformed gas outlet 8.

상기의 본 발명에 의한 메탄올개질장치의 실시예에 있어서 메탄올과 물을 몰비로 1 대 1.14로 공급하고 개질촉매로써 크기 4㎜ ×3㎜의 구리(Cu) - 아연(Zn)산화물 촉매를 사용하였을 때 생성된 개질가스는 Dry ase로 H267%, CO 0.7%, CO228.3%, CH44%의 조성을 나타내었으며, 이때 메탄올의 전환율은 95%이상 연소촉매층의 온도는 200 - 330℃의 분포를 기록하였다.In the embodiment of the methanol reformer according to the present invention, methanol and water were supplied at a molar ratio of 1 to 1.14, and a copper (Cu) -zinc (Zn) oxide catalyst having a size of 4 mm x 3 mm was used as the reforming catalyst. The reformed gas produced at the time of drying ase was composed of H 2 67%, CO 0.7%, CO 2 28.3%, and CH 4 4%, wherein the conversion rate of methanol was 95% or more and the temperature of the combustion catalyst bed was 200-330 ° C. The distribution was recorded.

이상에서와 같이 구성된 본 발명에 의한 메탄올개질장치를 이용한 고순도수소제조장치의 일례를 제 3도에 나타내었다.An example of the high purity hydrogen production apparatus using the methanol reformer according to the present invention configured as described above is shown in FIG.

제 3도에서 연소용공기는 송풍기(30)에 의해 개질장치(1)로 공급되며 연소용연료는 PSA 장치(24)의 오프가스(off gas) 탱크(25)에 저장된 수소포함가스가 일정유량으로 개질장치(1)로 유입되는데 최초 가동시 및 연소열량이 부족할 경우는 수소저장탱크(27)로 부터 고순도수소를 일부 연료로서 사용하게 된다. 개질가스 원료인 메탄올 및 물은 저장탱크(21)(22)및 펌프(28)(29)를 통하여 공급되며 열교환기(20)를 통과하면서 예열된 후 개질장치(1)로 유입된다.In FIG. 3, the combustion air is supplied to the reformer 1 by the blower 30, and the combustion fuel is a hydrogen-containing gas stored in the off gas tank 25 of the PSA device 24. Into the reformer 1, when the initial operation and the amount of heat of combustion is insufficient, high purity hydrogen is used as some fuel from the hydrogen storage tank 27. Methanol and water, which are reformed gas raw materials, are supplied through the storage tanks 21 and 22 and the pumps 28 and 29 and are preheated while passing through the heat exchanger 20 and then introduced into the reformer 1.

개질장치(1)를 통과한 개질가스는 열교환기(20) 및 기액분리기(23)를 통과한 후 PSA 장치(24)로 유입되어 고순도수소가 생산된다.The reformed gas that has passed through the reformer 1 passes through the heat exchanger 20 and the gas-liquid separator 23 and then flows into the PSA device 24 to produce high purity hydrogen.

PSA 장치(24)는 진공펌프(26)를 사용하여 재생하며 이때 탈착된 오프가스(Off gas)는 오프가스탱크(25)에 저장된다.The PSA device 24 is regenerated using the vacuum pump 26, and the desorbed off gas is stored in the off gas tank 25.

이상에서와 같이 본 발명에 의한 고순도수소제조를 위한 메탄올개질장치는 개질장치내에 다수의 원통형 연소촉매구조물 및 다공성 연료공급관을 설치하여 각 연소촉매층에서 균일한 연소반응이 일어날 수 있도록 함으로써 종래의 촉매연소방식에 비하여 연소실내의 온도를 낮게 유지, 운전할 수 있어 제품의 신뢰도 및 열효율을 향상시킬 수 있으며(아래 표 1에 표기됨) 개질장치의 운전온도 범위가 낮으므로 온도내구성이 낮은 개질촉매를 선정할 수 있어 제품의 경제성이 향상되며, 장치의 유지보수에 있어서는 특히 연소촉매층의 열화시 열화된 연소촉매층만 교체하면 되므로 유지보수가 간단하고 비용이 절감되는 잇점을 가지고 있다.As described above, the methanol reforming apparatus for producing high-purity hydrogen according to the present invention includes a plurality of cylindrical combustion catalyst structures and a porous fuel supply pipe in the reforming apparatus so that a uniform combustion reaction can occur in each combustion catalyst layer. Compared to this method, it is possible to maintain and operate the temperature in the combustion chamber lower, which can improve the reliability and thermal efficiency of the product (shown in Table 1 below), and the reforming catalyst with low temperature durability can be selected because the operating temperature range of the reforming device is low. The economical efficiency of the product can be improved, and the maintenance of the device has the advantage that the maintenance is simple and the cost is reduced because only the deteriorated combustion catalyst layer needs to be replaced, especially when the combustion catalyst layer is deteriorated.

[표 1]TABLE 1

제 1도는 종래기술에 의한 메탄올개질장치의 정단면도,1 is a front sectional view of a methanol reformer according to the prior art,

제 2도는 본 발명에 의한 메탄올개질장치의 정단면도,2 is a front sectional view of the methanol reformer according to the present invention,

제 3도는 본 발명에 의한 메탄올개질장치를 이용한 고순도수소제조장치 실시예의 개념도3 is a conceptual diagram of an embodiment of a high purity hydrogen production apparatus using a methanol reformer according to the present invention

*도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings

1 : 개질장치 2 : 연소촉매층1 reformer 2 combustion catalyst bed

3 : 연료공급관 4 : 원료기화코일3: fuel supply pipe 4: raw material vaporization coil

9 : 개질관9: reforming pipe

Claims (5)

개질촉매(10)가 충진된 이중원통형 단관식 개질관(9)을 설치된 개질장치에 있어서, 상기 개질관(9)의 내측에 하니컴 구조의 연소촉매층(2)을 다수 설치하고, 상기 연소촉매층(2) 중앙에 연료공급관(3)을 설치하며, 상기 개질관(9)의 내측에 원료기화코일(4)을 설치하여 개질관(9)에 연결한 것을 특징으로 하는 메탄올 개질장치.In the reforming apparatus provided with the double-cylinder type single tube reforming pipe (9) filled with the reforming catalyst (10), a plurality of honeycomb combustion catalyst layers (2) are provided inside the reforming pipe (9), and the combustion catalyst layer ( 2) A methanol reformer having a fuel supply pipe (3) in the center and a raw material vaporization coil (4) inside the reforming pipe (9) and connected to the reforming pipe (9). 제 1항에 있어서, 상기 연소촉매층(2)은 원통형 구조물에 연소촉매를 담지한 것으로서 개질관(9) 내측 연소실내에 수개의 일정간격을 두고 설치된 것을 특징으로 하는 메탄올 개질장치.2. The methanol reformer as set forth in claim 1, wherein said combustion catalyst layer (2) carries a combustion catalyst in a cylindrical structure and is installed at several predetermined intervals in a combustion chamber inside said reforming pipe (9). 제 1항에 있어서 연료공급관(3)에는 수십개의 연료분사공(13)을 하부에서 상부로 갈수록 점차적으로 많거나 크게 형성시켜 각 연소촉매층(2) 사이로 일정비율의 연료를 공급할 수 있도록 한 것을 특징으로 하는 메탄올 개질장치.The fuel supply pipe (3) according to claim 1, characterized in that dozens of fuel injection holes (13) are gradually formed in the fuel supply pipe (3) from the lower part to the upper part so as to supply a constant ratio of fuel between the respective combustion catalyst layers (2). Methanol reformer. 제 1항에 있어서 상기 연소촉매층(2) 사이 및 연료공급관(3) 주위로 원료기화코일(4)이 설치된 것을 특징으로 하는 메탄올 개질장치.The methanol reformer of claim 1, wherein a raw material vaporization coil (4) is provided between the combustion catalyst layers (2) and around a fuel supply pipe (3). 제 1항에 있ㅎ어서, 상기 개질장치(1)의 하단에 공기공급관(6) 및 연소용연료공급입구관(11)과 개질가스원료공급관(7) 및 개질가스출구(8)가 형성되고 개질장치 하부외측공간으로 연소가스출구(5)가 형성된 것을 특징으로 하는 메탄올 개질장치.According to claim 1, the air supply pipe 6 and the combustion fuel supply inlet pipe 11 and the reformed gas raw material supply pipe 7 and the reformed gas outlet 8 is formed at the lower end of the reforming device (1) Methanol reformer, characterized in that the combustion gas outlet (5) is formed in the lower outer space of the reformer.
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KR20220134205A (en) * 2021-03-26 2022-10-05 금오공과대학교 산학협력단 Electrochemical splitting device for producting hydrogen based on ethylene glycol and terephthalic acid, hydrogen production method and hydrogen production apparatus through electrochemical splitting using the same
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KR102576442B1 (en) * 2021-03-26 2023-09-07 금오공과대학교 산학협력단 Electrochemical splitting device for producting hydrogen based on ethylene glycol and terephthalic acid, hydrogen production method and hydrogen production apparatus through electrochemical splitting using the same
KR102576440B1 (en) * 2021-03-26 2023-09-07 금오공과대학교 산학협력단 Electrochemical splitting device for producting hydrogen based on methanol, hydrogen production method and hydrogen production apparatus through electrochemical splitting pure methanol using the same

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