WO2021075802A1 - Highly efficient steam-reforming hydrogen production apparatus with hydrodesulfurization - Google Patents

Highly efficient steam-reforming hydrogen production apparatus with hydrodesulfurization Download PDF

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WO2021075802A1
WO2021075802A1 PCT/KR2020/013827 KR2020013827W WO2021075802A1 WO 2021075802 A1 WO2021075802 A1 WO 2021075802A1 KR 2020013827 W KR2020013827 W KR 2020013827W WO 2021075802 A1 WO2021075802 A1 WO 2021075802A1
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heat exchanger
raw material
gas
hydrogen
heat
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French (fr)
Korean (ko)
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김명준
최준태
이재원
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주식회사 트리신
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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
    • C01B3/34—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
    • C01B3/48—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 followed by reaction of water vapour with carbon monoxide
    • 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
    • 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
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift 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
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/0425—In-situ adsorption process 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
    • 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
    • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
    • 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
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal 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
    • C01B2203/1076—Copper or zinc-based 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation

Definitions

  • Hydrogen production equipment is a device that supplies hydrogen or reforming gas (Reformate: H 2 , CO, CO 2 , CH 4 ), and is generally used to optimize raw material desulfurization equipment, steam reforming reactors, water gas reactors, and thermal energy of the process. It consists of a heat exchange network.
  • desulfurization performance must be excellent so that natural gas, LPG, naphtha, etc. can be used as raw materials.
  • Patent Document 1 Korean Patent Registration No. 130033
  • Patent Document 3 Korean Patent Publication No. 2007-0099644
  • the thermal efficiency was maximized, the desulfurization performance was enhanced, and a method of stably operating under a desired operating condition after the process operation was proposed.
  • a heat exchanger 1 for introducing a mixture of the desulfurized hydrocarbon raw material and the superheated steam into a reforming reactor by exchanging heat with the reformed gas discharged from the reforming reactor;
  • a heat exchanger 7 for exchanging heat with cooling water so that the converted gas generated from the water gas reactor is reduced to temperature before being introduced into the PSA;
  • the heat exchanger 6 for heat-exchanging the raw material moisture with the conversion gas to increase the temperature is substituted or further included in the heat exchanger 7.
  • the heat exchanger 6 is preferably disposed between the heat exchanger 5 and the heat exchanger 7.
  • the exhaust gas of the PSA is heated by the heat exchanger 5 disposed between the water gas reactor and the heat exchanger 7.
  • the heat exchangers 1 to 7 are a finned tube heat exchanger, a plate type heat exchanger, a multitube hairpin type, or a shell and tube type heat exchanger. It is desirable.
  • the hydrocarbon raw material is preferably a gaseous or liquid hydrocarbon including one or more of natural gas, LPG and Naphtha.
  • the catalyst filled in the catalytic reaction part is preferably ruthenium or nickel supported on an alumina or silica carrier.
  • the amount of raw material steam supplied to the reforming reactor is mixed in a ratio of 1:2.5 to 4.0 in a molar ratio of steam to carbon.
  • the desulfurization performance was enhanced by the hydrogen desulfurization method, and thermal efficiency was maximized by adding a heat exchanger, and stable operation was possible under desired operating conditions after the operation of the process.
  • a heat exchanger 1 for introducing a mixture of the desulfurized hydrocarbon raw material and the superheated steam into a reforming reactor by exchanging heat with the reformed gas discharged from the reforming reactor;
  • a heat exchanger 2 provided between the heat exchanger 1 and the heat exchanger 3 to raise the temperature of the mixture of the hydrocarbon raw material and the hydrogen recycled from the PSA through heat exchange with the reformed gas.
  • a hydrodesulfurizer for hydrodesulfurization of raw hydrocarbons A reforming reactor in which the raw material moisture mixed with the desulfurized hydrocarbon raw material is introduced from the hydrogen desulfurizer and heated by a burner to perform a steam reforming reaction; A water gas reactor for a water gas conversion reaction of carbon monoxide with respect to the reformed gas from the reforming reactor; And as a hydrogen production apparatus comprising a PSA for hydrogen separation,
  • a heat exchanger 4 for exchanging heat with the high-temperature exhaust gas discharged from the burner in order to overheat the raw material moisture with single-phase steam before mixing with the desulfurized hydrocarbon raw material;
  • a heat exchanger 1 for introducing a mixture of the desulfurized hydrocarbon raw material and the superheated steam into a reforming reactor by exchanging heat with the reformed gas discharged from the reforming reactor;
  • a heat exchanger 7 for exchanging heat with cooling water so that the converted gas generated from the water gas reactor is reduced to temperature before being introduced into the PSA;
  • It includes a heat exchanger 2 provided between the heat exchanger 1 and the heat exchanger 3 to raise the temperature of the mixture of the hydrocarbon raw material and the hydrogen recycled from the PSA through heat exchange with the reformed gas.
  • the heat exchanger 6 which replaces or additionally includes the heat exchanger 7 by heat-exchanging the raw material moisture, for example, deionized water with a conversion gas.
  • the heat exchanger 6 is disposed between the heat exchanger 5 and the heat exchanger 7.
  • the hydrogen production apparatus of the present invention it is preferable that a part of the hydrocarbon raw material not supplied to the hydrogen desulfurizer, air heated in the heat exchanger 3, and exhaust gas of the PSA are supplied to the burner.
  • the exhaust gas of the PSA is heated by a heat exchanger 5 disposed between the water gas reactor and the heat exchanger 7.
  • the heat exchangers 1 to 7 are a finned tube heat exchanger, a plate type heat exchanger, a multitube hairpin type, or a shell and tube type heat exchanger. I can. More preferably, a multitube hairpin type heat exchanger equipped with a finned tube and a twisted tape vortex generator with a true counter current method is preferred. Can be used.
  • the hydrocarbon raw material may be a gaseous or liquid hydrocarbon including natural gas, LPG, and naphtha.
  • natural gas may be used, and the natural gas is divided into two parts: a raw material (Feed) and a fuel (Fuel), and the raw material is supplied to the hydrogen desulfurizer, and the fuel is supplied to the burner.
  • the hydrocarbon raw material supplied to the hydrogen desulfurizer is mixed with hydrogen recycled from the PSA, and heated by heat exchange with the reformed gas in the heat exchanger 2 disposed between the heat exchanger 1 and the heat exchanger 3.
  • the main component in the catalyst poison of the reforming reactor and the water gas reactor catalyst is the sulfur component. Therefore, the sulfur component in natural gas or LPG, which is a raw material for reaction, must be completely removed.
  • the sulfur component in natural gas is easily removed by the physical adsorbent at room temperature. However, the sulfur component inside LPG is not removed by physical adsorption.
  • the sulfur component was converted to hydrogen sulfide by hydrogen desulfurization reaction using hydrogen, and then the sulfur component was completely removed using a chemical adsorbent such as ZnO.
  • a chemical adsorbent such as ZnO.
  • the hydrogen desulfurization catalyst used for example, metals such as cobalt, zinc, copper, molybdenum, nickel, metal oxides or emulsions, zeolite or activated carbon, etc. can be used. Hydrodesulfurization is carried out at temperature.
  • This hydrodesulfurization method has superior performance compared to the physical adsorption method, so that even a compact adsorption device can obtain an equal or higher effect.
  • the reaction raw material is mixed after recycling a part of the produced hydrogen, heated to 300°C, which is the operating temperature of the hydrogen desulfurizer through heat exchanger 2, and then enters the hydrogen desulfurizer and desulfurizes.
  • the amount of hydrogen used is 10 to 500 times the sulfur content of the raw material, and the amount of recirculation can be adjusted according to the sulfur content of the raw material.
  • the desulfurized raw material is mixed with steam passing through heat exchanger 4, heat-exchanging with reformate 1 in heat exchanger 1 to heat up and enter the reforming reactor.
  • the desulfurized reaction raw material and the raw material steam are mixed and supplied.
  • the raw material steam is 160-350°C by heat exchange using the combustion exhaust gas of the reforming reactor burner and heat exchanger 4 to superheat the demineralized water into single-phase steam. It can be preheated using a heat exchanger 6 in order to generate steam overheated by furnace, and to further increase thermal efficiency and stably generate steam.
  • Heat exchanger 6 maximizes thermal efficiency by exchanging demineralized water at room temperature with conversion gas (Reformate 2) and preheating it to 40 ⁇ 100°C.
  • the desulfurized raw material and raw material steam are mixed, it is heat-exchanged with the high-temperature reforming gas (Reformate 1) from the reforming reactor, and heated to 400 to 600°C and supplied to the reforming reactor.
  • Reformate 1 the high-temperature reforming gas
  • the moisture of the raw material contained in the raw material by the heating by heat exchange as described above does not flow into the reforming reactor in a state separated into two phases of a liquid phase and a gaseous phase. It was introduced and designed to provide optimum reaction conditions for the reforming catalyst.
  • the amount of raw material steam supplied to the reforming reactor is preferably mixed in a ratio of steam to carbon molar ratio (S/C) 1:2.5 to 4.0, where the S/C ratio is less than 2.5.
  • the reforming catalyst is poisoned by carbon due to insufficient water vapor, resulting in deterioration of performance. If it exceeds 4.0, it is not preferable because there is a problem in that thermal efficiency is lowered due to excessive injection of water vapor.
  • the mixture is brought into contact with a reforming catalyst and steam reformed to produce a gas containing a high concentration of hydrogen.
  • a burner for heating the reforming reactor from the outside is provided below the reforming reactor.
  • the reforming reactor includes a catalyst filled to allow the mixture to flow, and the filled catalyst is preferably ruthenium or nickel supported on an alumina or silica carrier.
  • the reforming reactor is heated and heated by a burner, and the operating temperature is maintained at 700 to 850°C in order to supply the reaction heat required for the catalytic reaction.
  • the temperature of the exhaust gas discharged by heating the reforming reactor is 600 to 700°C, and is introduced into the heat exchanger 4, and the reforming gas (CO, CO 2 , CH 4 , H 2 ) converted through the reforming reaction is 500 to 600 It is introduced into the water gas reactor through heat exchangers 1 to 3 at a temperature of °C.
  • the reformed gas is heat-exchanged with the raw material of the reforming reactor in heat exchanger 1 to lower the temperature, and after supplying heat to the hydrogen desulfurizer raw material through heat exchanger 2, the air supplied from heat exchanger 3 to the burner is preheated to finally It is adjusted to 170°C ⁇ 200°C, which is a suitable temperature for the water gas reactor.
  • the water gas reaction is thermodynamically better as the temperature is lower, but if the temperature is too low, the reaction rate becomes slow. Therefore, the reformed gas is allowed to start reaction in the water gas reactor at 170°C to 200°C.
  • the water gas conversion reaction in the water gas reactor is known in the art, and consists of CO + H 2 O ⁇ CO 2 + H 2.
  • the water gas reactor is filled with a water gas conversion catalyst for converting carbon monoxide in the reformed gas into carbon dioxide and hydrogen, and as the water gas conversion catalyst, an oxide catalyst such as iron-chromium or copper-zinc system may be preferably used.
  • the water gas reaction is an exothermic reaction and thermodynamically, the lower the temperature is, the better, so the reactor outlet temperature should be adjusted to 265°C or less.
  • the conversion gas (Reformate 2) generated in the water gas reactor is heat-exchanged with the cooling water in the heat exchanger 7 to be adjusted to a temperature suitable for PSA introduction.
  • the conversion gas from the water gas reactor is generally 250 ⁇ 260 °C, but in the case of the PSA, which is a hydrogen separation device connected to the rear stage, the separation efficiency is better as the temperature of the conversion gas is lower and 40 °C or less.
  • the PSA which is a hydrogen separation device connected to the rear stage
  • the separation efficiency is better as the temperature of the conversion gas is lower and 40 °C or less.
  • a heat exchanger 7 is usually used to lower the temperature with cooling water. In this case, the heat energy held by the converted gas is wasted.
  • heat exchanger 5 the PSA exhaust gas used as fuel for the reformer burner was able to recover some heat from the conversion gas.
  • the hydrogen production apparatus of the present invention further includes a heat exchanger 5 between the water gas reactor and the heat exchanger 7, and heat-exchanges the PSA exhaust gas with the conversion gas to increase the temperature.
  • the hydrogen production apparatus of the present invention further includes a heat exchanger 6 for heat-exchanging the demineralized water with a conversion gas to raise the temperature.
  • the heat exchanger 6 is preferably disposed between the heat exchanger 5 and the heat exchanger 7.
  • the PSA exhaust gas preheated in the heat exchanger 5 is configured to be supplied to the burner of the reformer reactor to recover heat.
  • the material supplied to the burner of the reforming reactor is composed of natural gas, LPG, etc., which are fuels, air heated in heat exchanger 3, and PSA exhaust gas heated in heat exchanger 5.
  • PSA Pressure Swing Adsorption
  • PSA Pressure Swing Adsorption
  • the high-purity hydrogen separated from the PSA can be stored in a hydrogen storage tank and used or connected without a storage device to be used as hydrogen fuel for fuel cells or hydrogen electric vehicles, and the exhaust gas from the PSA is used as fuel for the burner for heating the reforming reactor. It is recycled to maximize thermal efficiency.
  • the present invention relates to a hydrogen production apparatus in which thermal efficiency is maximized and desulfurization performance is enhanced in a hydrogen production process by steam reforming.

Abstract

Hydrogen production thermal efficiency is very important for a small hydrogen production apparatus used in a fuel cell, a hydrogen station, etc., unlike a large-scale plant for producing hydrogen. In addition, frequent operation stops and restarts due to characteristics of the apparatus need not only the ease of operation but also require that a post-operation process should quickly reach a desired condition and be stabilized. Furthermore, excellent desulfurization performance is required in order to use natural gas, LPG, naphtha, etc. as raw materials. The present invention suggests a method in which thermal efficiency is maximized, desulfurization performance is enhanced, and desired operation conditions can be quickly achieved after operating a process.

Description

수소탈황을 구비한 고효율 스팀 리포밍 수소 제조 장치High-efficiency steam reforming hydrogen production device with hydrogen desulfurization
본 발명은 스팀 개질에 의한 수소 제조 공정에 있어서 열효율이 극대화되고 탈황 성능이 강화된 수소 제조 장치에 관한 것이다.The present invention relates to a hydrogen production apparatus in which thermal efficiency is maximized and desulfurization performance is enhanced in a hydrogen production process by steam reforming.
수소 제조 장치는 수소나 개질가스(Reformate : H 2, CO, CO 2, CH 4)를 공급하는 장치로서, 일반적으로 원료 탈황 장치, 스팀 개질 반응기, 수성 가스 반응기, 그리고 공정의 열에너지를 최적화하기 위한 열교환 망으로 이루어진다. Hydrogen production equipment is a device that supplies hydrogen or reforming gas (Reformate: H 2 , CO, CO 2 , CH 4 ), and is generally used to optimize raw material desulfurization equipment, steam reforming reactors, water gas reactors, and thermal energy of the process. It consists of a heat exchange network.
수소를 제조하는 대형플랜트와 다르게, 연료전지나 수소스테이션 등에 쓰이는 소형 수소 제조 장치는 수소 제조 열효율이 매우 중요하다.Unlike large plants that produce hydrogen, the thermal efficiency of hydrogen production is very important in small hydrogen production equipment used in fuel cells or hydrogen stations.
또한, 장치 특성상 빈번한 운전 정지 및 재가동 때문에 운전 용이성뿐만 아니라 운전 가동 후 공정이 원하는 조건에 빠르게 도달되어 안정되어 한다. In addition, due to frequent operation stop and restart due to the characteristics of the device, not only operation is easy, but the process after operation is quickly reached and stabilized.
그리고 천연가스, LPG, 나프타 등을 원료로 사용할 수 있도록 탈황 성능도 우수해야 한다.In addition, desulfurization performance must be excellent so that natural gas, LPG, naphtha, etc. can be used as raw materials.
이에 따라, 아래 특허문헌들과 같이 수소 제조 장치의 변형 또는 배치와, 다양한 열교환망 및 유로 구성을 시도하였으나, 전체 수소 제조 장치의 탈황성능, 안정성 및 효율성 측면에서 여전히 미흡한 실정이었다.Accordingly, modifications or arrangements of the hydrogen production apparatus and various heat exchange networks and flow channels were attempted as in the following patent documents, but the situation was still insufficient in terms of desulfurization performance, stability, and efficiency of the entire hydrogen production apparatus.
(선행문헌)(Priority literature)
(특허문헌 1) 한국 특허등록번호 제130033호(Patent Document 1) Korean Patent Registration No. 130033
(특허문헌 2) 한국 특허등록번호 제1832136호(Patent Document 2) Korean Patent Registration No. 1832136
(특허문헌 3) 한국 특허공개번호 제2007-0099644호(Patent Document 3) Korean Patent Publication No. 2007-0099644
본 발명에서는 열효율을 극대화하였고, 탈황 성능을 강화하였으며, 또한 공정 가동 후 원하는 운전 조건에서 안정적으로 운전이 가능한 방안을 제시하였다.In the present invention, the thermal efficiency was maximized, the desulfurization performance was enhanced, and a method of stably operating under a desired operating condition after the process operation was proposed.
상기 과제를 해결하기 위한 본 발명에 따른 수소 제조 장치는,Hydrogen production apparatus according to the present invention for solving the above problems,
원료 탄화수소를 수첨탈황시키는 수소탈황기; 상기 수소탈황기로부터 탈황된 탄화수소 원료와 혼합된 원료수분이 도입되고, 버너에 의하여 가열되어 수증기 개질반응이 이루어지는 개질반응기; 상기 개질반응기로부터의 개질 가스에 대하여 일산화탄소의 수성가스 전환 반응을 위한 수성가스반응기; 및 수소 분리를 위한 PSA(압력스윙흡착)를 포함하며,Hydrodesulfurization group for hydrodesulfurization of raw hydrocarbons; A reforming reactor in which the raw material moisture mixed with the desulfurized hydrocarbon raw material is introduced from the hydrogen desulfurizer and heated by a burner to perform a steam reforming reaction; A water gas reactor for a water gas conversion reaction of carbon monoxide with respect to the reformed gas from the reforming reactor; And PSA (pressure swing adsorption) for hydrogen separation,
상기 탈황된 탄화수소 원료와 혼합시키기 전에 상기 원료수분을 단일 상의 수증기로 과열시키기 위하여, 상기 버너로부터 배출되는 연소배가스와 열교환시키는 열교환기 4;A heat exchanger 4 for exchanging heat with the combustion exhaust gas discharged from the burner in order to overheat the raw material moisture with steam in a single phase before mixing with the desulfurized hydrocarbon raw material;
상기 탈황된 탄화수소 원료와 상기 과열된 수증기의 혼합물을 상기 개질반응기로부터 배출되는 개질가스와 열교환시켜 개질반응기로 도입시키는 열교환기 1;A heat exchanger 1 for introducing a mixture of the desulfurized hydrocarbon raw material and the superheated steam into a reforming reactor by exchanging heat with the reformed gas discharged from the reforming reactor;
상기 열교환기 1을 거친 개질가스가 상기 수성가스반응기로 도입되기 전에 감온되도록, 외부 공기와 열교환시키는 열교환기 3;A heat exchanger 3 for exchanging heat with external air so that the reformed gas passing through the heat exchanger 1 is reduced to temperature before being introduced into the water gas reactor;
상기 수성가스반응기부터 생성된 전환가스가 상기 PSA로 도입되기 전에 감온되도록, 냉각수와 열교환시키는 열교환기 7; 및A heat exchanger 7 for exchanging heat with cooling water so that the converted gas generated from the water gas reactor is reduced to temperature before being introduced into the PSA; And
탄화수소 원료와 상기 PSA로부터 재순환된 수소의 혼합물을 개질가스와의 열교환으로 승온시키기 위해, 상기 열교환기 1 및 열교환기 3의 사이에 구비된 Provided between the heat exchanger 1 and the heat exchanger 3 to raise the temperature of the mixture of the hydrocarbon raw material and the hydrogen recycled from the PSA by heat exchange with the reformed gas.
열교환기 2;를 포함한다. Heat exchanger 2; includes.
상기 수성가스반응기와 열교환기 7의 사이에 배치되어, 상기 PSA의 배가스를 상기 전환가스와 열교환시켜 승온시키는 열교환기 5를 추가로 포함하는 것이 바람직하다.It is preferable to further include a heat exchanger 5 disposed between the water gas reactor and the heat exchanger 7 to heat-exchange the exhaust gas of the PSA with the conversion gas to increase temperature.
상기 원료수분을 전환가스와 열교환시켜 승온시키는 열교환기 6이 열교환기 7을 대체하거나 추가로 포함되는 것이 보다 바람직하다.It is more preferable that the heat exchanger 6 for heat-exchanging the raw material moisture with the conversion gas to increase the temperature is substituted or further included in the heat exchanger 7.
상기 열교환기 6은 열교환기 5와 열교환기 7의 사이에 배치되는 것이 바람직하다.The heat exchanger 6 is preferably disposed between the heat exchanger 5 and the heat exchanger 7.
상기 탄화수소 원료의 일부, 상기 열교환기 3에서 승온된 공기, 및 상기 PSA의 배가스가 상기 버너에 공급되는 것이 바람직하다.It is preferable that a part of the hydrocarbon raw material, air heated in the heat exchanger 3, and exhaust gas of the PSA are supplied to the burner.
상기 PSA의 배가스가 상기 수성가스반응기와 열교환기 7의 사이에 배치된 열교환기 5에 의해 승온되는 것이 바람직하다.It is preferable that the exhaust gas of the PSA is heated by the heat exchanger 5 disposed between the water gas reactor and the heat exchanger 7.
상기 열교환기 1 내지 7은 핀 튜브 형태(Finned tube) 열교환기, 판상 열교환기(Plate type heat exchanger), 멀티튜브 헤어핀 형(Multitube hairpin type) 또는 셀 앤드 튜브 형태(Shell and tube type)의 열교환기인 것이 바람직하다.The heat exchangers 1 to 7 are a finned tube heat exchanger, a plate type heat exchanger, a multitube hairpin type, or a shell and tube type heat exchanger. It is desirable.
상기 탄화수소 원료는 천연가스, LPG 및 나프타(Naphtha)를 하나 이상 포함한 기상 또는 액상 탄화수소인 것이 바람직하다.The hydrocarbon raw material is preferably a gaseous or liquid hydrocarbon including one or more of natural gas, LPG and Naphtha.
상기 개질반응기는 상기 혼합물이 유동 가능하도록 촉매를 충진한 촉매 반응부를 포함하며,The reforming reactor includes a catalytic reaction unit filled with a catalyst to allow the mixture to flow,
상기 촉매 반응부에 충진된 촉매는 루테늄(ruthenium) 또는 니켈을 알루미나(alumina) 또는 실리카(silica) 담체에 담지시킨 것이 바람직하다.The catalyst filled in the catalytic reaction part is preferably ruthenium or nickel supported on an alumina or silica carrier.
상기 수소탈황기내의 촉매는 코발트, 아연, 동, 몰리브덴 및 니켈로부터 선택된 하나 이상의 금속이나 금속산화물 또는 유화물; 제오라이트; 또는 활성탄을 포함하는 것이 바람직하다.The catalyst in the hydrogen desulfurization group may include at least one metal or metal oxide or emulsion selected from cobalt, zinc, copper, molybdenum, and nickel; Zeolite; Or it is preferable to include activated carbon.
상기 개질반응기로 공급되는 원료수증기의 양은 수증기 대 탄소 몰비가 1:2.5~4.0의 비율로 혼합되는 것이 바람직하다.It is preferable that the amount of raw material steam supplied to the reforming reactor is mixed in a ratio of 1:2.5 to 4.0 in a molar ratio of steam to carbon.
상기 수성가스반응기내의 촉매는 철-크롬계 촉매 또는 동-아연계 촉매인 것이 바람직하다.The catalyst in the water gas reactor is preferably an iron-chromium-based catalyst or a copper-zinc catalyst.
본 발명에서는 수소 탈황 방법으로 탈황 성능을 강화하였으며 또한 열교환기를 추가하여 열효율을 극대화하였고, 또한 공정 가동 후에 원하는 운전 조건에서 안정적인 운전이 가능하였다.In the present invention, the desulfurization performance was enhanced by the hydrogen desulfurization method, and thermal efficiency was maximized by adding a heat exchanger, and stable operation was possible under desired operating conditions after the operation of the process.
도 1은 본 발명에 따른 수소 제조 장치의 일례를 개략적으로 도시한 것이다.1 schematically shows an example of an apparatus for producing hydrogen according to the present invention.
본 발명에 따른 수소 제조 장치는,The hydrogen production apparatus according to the present invention,
원료 탄화수소를 수첨탈황시키는 수소탈황기; 상기 수소탈황기로부터 탈황된 탄화수소 원료와 혼합된 원료수분이 도입되고, 버너에 의하여 가열되어 수증기 개질반응이 이루어지는 개질반응기; 상기 개질반응기로부터의 개질 가스에 대하여 일산화탄소의 수성가스 전환 반응을 위한 수성가스반응기; 및 수소 분리를 위한 PSA(압력스윙흡착)를 포함하며,Hydrodesulfurization group for hydrodesulfurization of raw hydrocarbons; A reforming reactor in which the raw material moisture mixed with the desulfurized hydrocarbon raw material is introduced from the hydrogen desulfurizer and heated by a burner to perform a steam reforming reaction; A water gas reactor for a water gas conversion reaction of carbon monoxide with respect to the reformed gas from the reforming reactor; And PSA (pressure swing adsorption) for hydrogen separation,
상기 탈황된 탄화수소 원료와 혼합시키기 전에 상기 원료수분을 단일 상의 수증기로 과열시키기 위하여, 상기 버너로부터 배출되는 연소배가스와 열교환시키는 열교환기 4;A heat exchanger 4 for exchanging heat with the combustion exhaust gas discharged from the burner in order to overheat the raw material moisture with steam in a single phase before mixing with the desulfurized hydrocarbon raw material;
상기 탈황된 탄화수소 원료와 상기 과열된 수증기의 혼합물을 상기 개질반응기로부터 배출되는 개질가스와 열교환시켜 개질반응기로 도입시키는 열교환기 1;A heat exchanger 1 for introducing a mixture of the desulfurized hydrocarbon raw material and the superheated steam into a reforming reactor by exchanging heat with the reformed gas discharged from the reforming reactor;
상기 열교환기 1을 거친 개질가스가 상기 수성가스반응기로 도입되기 전에 감온되도록, 외부 공기와 열교환시키는 열교환기 3;A heat exchanger 3 for exchanging heat with external air so that the reformed gas passing through the heat exchanger 1 is reduced to temperature before being introduced into the water gas reactor;
상기 수성가스반응기부터 생성된 전환가스가 상기 PSA로 도입되기 전에 감온되도록, 냉각수와 열교환시키는 열교환기 7; 및A heat exchanger 7 for exchanging heat with cooling water so that the converted gas generated from the water gas reactor is reduced to temperature before being introduced into the PSA; And
탄화수소 원료와 상기 PSA로부터 재순환된 수소의 혼합물을 개질가스와의 열교환으로 승온시키기 위해, 상기 열교환기 1 및 열교환기 3의 사이에 구비된 열교환기 2;를 포함한다.And a heat exchanger 2 provided between the heat exchanger 1 and the heat exchanger 3 to raise the temperature of the mixture of the hydrocarbon raw material and the hydrogen recycled from the PSA through heat exchange with the reformed gas.
이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시 형태를 설명한다. 그러나, 본 발명의 실시 형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다. Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, embodiments of the present invention may be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.
본 실시예들을 설명함에 있어서, 동일 구성에 대해서는 동일 명칭 및 부호가 사용되며, 이에 따라 중복되는 부가적인 설명은 아래에서 생락된다. 아래에서 참조되는 도면들에서는 축적비가 적용되지 않는다.In describing the present embodiments, the same names and symbols are used for the same configuration, and therefore, duplicated additional descriptions are omitted below. In the drawings referred to below, the accumulation ratio is not applied.
본 발명의 수소제조장치는 수소나 개질가스(H 2, CO, CO 2, CH 4)를 제조하는 장치로서, 일반적으로 원료 탄화수소를 수첨 탈황시키는 수소탈황기, 수소탈황기로부터 탈황된 탄화수소 원료와 혼합된 원료 수분이 도입되고, 연소에 의하여 가열되어 스팀개질반응이 이루어지는 개질반응기, 상기 개질반응기에서 나온 개질가스에 대하여 일산화탄소의 수성가스 전환 반응을 위한 수성가스반응기, 수소 분리를 위한 PSA 그리고 공정의 열에너지를 최적화하기 위한 열교환 망으로 이루어진다.The hydrogen production apparatus of the present invention is an apparatus for producing hydrogen or reforming gas (H 2 , CO, CO 2 , CH 4 ). In general, a hydrogen desulfurizer for hydrodesulfurization of raw hydrocarbons, a hydrocarbon raw material desulfurized from a hydrogen desulfurization A reforming reactor in which the mixed raw material moisture is introduced and heated by combustion to perform a steam reforming reaction, a water gas reactor for a water gas conversion reaction of carbon monoxide to the reformed gas from the reforming reactor, a PSA for hydrogen separation, and a process It consists of a heat exchange network to optimize thermal energy.
구체적으로 도 1을 참조하여 설명하면, 원료 탄화수소를 수첨탈황시키는 수소탈황기; 상기 수소탈황기로부터 탈황된 탄화수소 원료와 혼합된 원료수분이 도입되고, 버너에 의하여 가열되어 수증기 개질반응이 이루어지는 개질반응기; 상기 개질반응기로부터의 개질 가스에 대하여 일산화탄소의 수성가스 전환 반응을 위한 수성가스반응기; 및 수소 분리를 위한 PSA를 포함하는 수소 제조 장치로서,Specifically, referring to FIG. 1, a hydrodesulfurizer for hydrodesulfurization of raw hydrocarbons; A reforming reactor in which the raw material moisture mixed with the desulfurized hydrocarbon raw material is introduced from the hydrogen desulfurizer and heated by a burner to perform a steam reforming reaction; A water gas reactor for a water gas conversion reaction of carbon monoxide with respect to the reformed gas from the reforming reactor; And as a hydrogen production apparatus comprising a PSA for hydrogen separation,
상기 탈황된 탄화수소 원료와 혼합시키기 전에 상기 원료 수분을 단일 상의 수증기로 과열시키기 위하여, 상기 버너로부터 배출되는 고온의 배기 가스와 열교환시키는 열교환기 4;A heat exchanger 4 for exchanging heat with the high-temperature exhaust gas discharged from the burner in order to overheat the raw material moisture with single-phase steam before mixing with the desulfurized hydrocarbon raw material;
상기 탈황된 탄화수소 원료와 상기 과열된 수증기의 혼합물을 상기 개질반응기로부터 배출되는 개질가스와 열교환시켜 개질반응기로 도입시키는 열교환기 1;A heat exchanger 1 for introducing a mixture of the desulfurized hydrocarbon raw material and the superheated steam into a reforming reactor by exchanging heat with the reformed gas discharged from the reforming reactor;
상기 열교환기 1을 거친 개질가스가 상기 수성가스반응기로 도입되기 전에 감온되도록, 외부 공기와 열교환시키는 열교환기 3;A heat exchanger 3 for exchanging heat with external air so that the reformed gas passing through the heat exchanger 1 is reduced to temperature before being introduced into the water gas reactor;
상기 수성가스반응기로부터 생성된 전환가스가 상기 PSA로 도입되기 전에 감온되도록, 냉각수와 열교환시키는 열교환기 7; 및A heat exchanger 7 for exchanging heat with cooling water so that the converted gas generated from the water gas reactor is reduced to temperature before being introduced into the PSA; And
탄화수소 원료와 상기 PSA로부터 재순환된 수소의 혼합물을 개질가스와의 열교환으로 승온시키기 위해, 상기 열교환기 1 및 열교환기 3의 사이에 구비된 열교환기 2를 포함한다.It includes a heat exchanger 2 provided between the heat exchanger 1 and the heat exchanger 3 to raise the temperature of the mixture of the hydrocarbon raw material and the hydrogen recycled from the PSA through heat exchange with the reformed gas.
나아가, 본 발명의 수소 제조 장치는 상기 수성가스반응기와 열교환기 7의 사이에 배치되어 상기 PSA의 배가스를 상기 전환가스와 열교환시켜 승온시키는 열교환기 5를 추가로 포함하는 것이 바람직하다.Further, it is preferable that the hydrogen production apparatus of the present invention further includes a heat exchanger 5 disposed between the water gas reactor and the heat exchanger 7 to heat-exchange the exhaust gas of the PSA with the conversion gas to increase temperature.
또한, 본 발명의 수소 제조 장치는 상기 원료수분, 예를 들어 탈염수를 전환가스와 열교환시켜 승온시키는 열교환기 6이 열교환기 7을 대체하거나 추가로 포함되는 것이 보다 바람직하다.In addition, in the hydrogen production apparatus of the present invention, it is more preferable that the heat exchanger 6 which replaces or additionally includes the heat exchanger 7 by heat-exchanging the raw material moisture, for example, deionized water with a conversion gas.
이 경우, 상기 열교환기 6은 열교환기 5와 열교환기 7의 사이에 배치되는 것이 더욱 바람직하다.In this case, it is more preferable that the heat exchanger 6 is disposed between the heat exchanger 5 and the heat exchanger 7.
본 발명의 수소 제조 장치는 수소탈황기로 공급되지 않는 상기 탄화수소 원료의 일부, 상기 열교환기 3에서 승온된 공기, 및 상기 PSA의 배가스가 상기 버너에 공급되는 것이 바람직하다.In the hydrogen production apparatus of the present invention, it is preferable that a part of the hydrocarbon raw material not supplied to the hydrogen desulfurizer, air heated in the heat exchanger 3, and exhaust gas of the PSA are supplied to the burner.
이 경우, 상기 PSA의 배가스는 상기 수성가스반응기와 열교환기 7의 사이에 배치된 열교환기 5에 의해 승온되는 것이 바람직하다.In this case, it is preferable that the exhaust gas of the PSA is heated by a heat exchanger 5 disposed between the water gas reactor and the heat exchanger 7.
상기 열교환기 1 내지 7은 핀 튜브 형태(Finned tube) 열교환기, 판상 열교환기(Plate type heat exchanger), 멀티튜브 헤어핀 형(Multitube hairpin type) 또는 셀 앤드 튜브 형태(Shell and tube type)의 열교환기일 수 있다. 더욱 바람직하게는 트루 카운터 커런트(True counter current)방식을 구비한 핀 튜브(Finned tube), 트위스티드 테잎 보어텍스 제너레이터(Twisted tape vortex generator)를 구비한 멀티튜브 헤어핀 형(Multitube hairpin type) 열교환기가 바람직하게 사용될 수 있다.The heat exchangers 1 to 7 are a finned tube heat exchanger, a plate type heat exchanger, a multitube hairpin type, or a shell and tube type heat exchanger. I can. More preferably, a multitube hairpin type heat exchanger equipped with a finned tube and a twisted tape vortex generator with a true counter current method is preferred. Can be used.
상기 탄화수소 원료는 천연가스, LPG, 나프타(Naphtha) 등을 포함한 기상 또는 액상 탄화수소일 수 있다. 바람직하게는 천연가스가 사용될 수 있으며, 상기 천연가스는 원료(Feed) 및 연료(Fuel)의 두 부분으로 나누어져, 원료는 수소탈황기에 제공되며, 연료는 버너에 제공된다.The hydrocarbon raw material may be a gaseous or liquid hydrocarbon including natural gas, LPG, and naphtha. Preferably, natural gas may be used, and the natural gas is divided into two parts: a raw material (Feed) and a fuel (Fuel), and the raw material is supplied to the hydrogen desulfurizer, and the fuel is supplied to the burner.
상기 수소탈황기에 공급되는 탄화수소 원료는 PSA로부터 재순환되는 수소와 혼합되어, 열교환기 1과 열교환기 3의 사이에 배치된 열교환기 2에서 개질가스와의 열교환으로 승온된다.The hydrocarbon raw material supplied to the hydrogen desulfurizer is mixed with hydrogen recycled from the PSA, and heated by heat exchange with the reformed gas in the heat exchanger 2 disposed between the heat exchanger 1 and the heat exchanger 3.
개질반응기와 수성가스반응기 촉매의 촉매 독 중에 주요한 성분은 황 성분이다. 따라서, 반응원료인 천연가스나 LPG 내의 황성분을 완전하게 제거해야 한다. 천연가스 중의 황성분은 상온에서 물리적 흡착제에 용이하게 제거된다. 그러나 LPG 내부의 황성분은 물리적인 흡착에 의해서 제거가 되지 않는다. The main component in the catalyst poison of the reforming reactor and the water gas reactor catalyst is the sulfur component. Therefore, the sulfur component in natural gas or LPG, which is a raw material for reaction, must be completely removed. The sulfur component in natural gas is easily removed by the physical adsorbent at room temperature. However, the sulfur component inside LPG is not removed by physical adsorption.
본 발명에서는 수소를 사용하는 수소탈황반응에 의해서 황 성분을 황화수소로 전환한 후, ZnO 같은 화학적 흡착제를 사용하여 황성분을 완전하게 제거하였다. 이 경우 사용되는 수소탈황촉매로서 예를 들어 코발트, 아연, 동, 몰리브덴, 니켈 등의 금속이나 금속산화물 또는 유화물, 제오라이트나 활성탄 등이 사용될 수 있으며, 반응원료나 공정조건에 따라 150~400℃의 온도에서 수첨탈황을 수행한다.In the present invention, the sulfur component was converted to hydrogen sulfide by hydrogen desulfurization reaction using hydrogen, and then the sulfur component was completely removed using a chemical adsorbent such as ZnO. In this case, as the hydrogen desulfurization catalyst used, for example, metals such as cobalt, zinc, copper, molybdenum, nickel, metal oxides or emulsions, zeolite or activated carbon, etc. can be used. Hydrodesulfurization is carried out at temperature.
이와 같은 수소탈황 방법은 물리적 흡착방법 대비 성능이 우수하여 컴팩트한 흡착장치에서도 동등 이상의 효과를 얻을 수 있다. 도 1에 나타낸 바와 같이, 반응원료는 생산된 수소의 일부를 재순환시킨 후 혼합되고, 열교환기 2를 통하여 수소탈황기의 작동온도인 300℃로 가열된 후 수소탈황기로 들어가서 탈황된다. This hydrodesulfurization method has superior performance compared to the physical adsorption method, so that even a compact adsorption device can obtain an equal or higher effect. As shown in Fig. 1, the reaction raw material is mixed after recycling a part of the produced hydrogen, heated to 300°C, which is the operating temperature of the hydrogen desulfurizer through heat exchanger 2, and then enters the hydrogen desulfurizer and desulfurizes.
이때 사용되는 수소의 양은 원료의 황 함량 기준으로 10~500배를 사용하며, 원료의 황 함량에 따라 재순환 양의 조절이 가능하다. At this time, the amount of hydrogen used is 10 to 500 times the sulfur content of the raw material, and the amount of recirculation can be adjusted according to the sulfur content of the raw material.
탈황된 원료는 열교환기 4를 거친 수증기와 혼합된 후 열교환기 1에서 개질가스(Reformate 1)와 열교환하여 승온된 후 개질반응기로 들어간다.The desulfurized raw material is mixed with steam passing through heat exchanger 4, heat-exchanging with reformate 1 in heat exchanger 1 to heat up and enter the reforming reactor.
개질반응기에는 탈황된 반응원료와 원료인 수증기를 혼합하여 공급하게 되는데, 원료 수증기는 탈염수를 단일 상의 수증기로 과열시키기 위하여, 개질반응기 버너의 연소배가스와 열교환기 4를 이용하여 열교환하여 160~350℃로 과열된 수증기를 만들며, 추가로 열효율을 높이고 안정적으로 수증기를 생성하기 위하여 열교환기 6을 이용하여 예열할 수 있다. 열교환기 6에서는 상온의 탈염수를 전환가스(Reformate 2)와 열교환시켜 40~100℃로 예열함으로써 열효율을 극대화한다.To the reforming reactor, the desulfurized reaction raw material and the raw material steam are mixed and supplied.The raw material steam is 160-350℃ by heat exchange using the combustion exhaust gas of the reforming reactor burner and heat exchanger 4 to superheat the demineralized water into single-phase steam. It can be preheated using a heat exchanger 6 in order to generate steam overheated by furnace, and to further increase thermal efficiency and stably generate steam. Heat exchanger 6 maximizes thermal efficiency by exchanging demineralized water at room temperature with conversion gas (Reformate 2) and preheating it to 40~100℃.
탈황된 원료와 원료 수증기는 혼합된 후 개질반응기에서 나오는 고온의 개질가스(Reformate 1)와 열교환기 1에서 열교환되어 400~600℃로 가열되어 개질반응기로 공급된다.After the desulfurized raw material and raw material steam are mixed, it is heat-exchanged with the high-temperature reforming gas (Reformate 1) from the reforming reactor, and heated to 400 to 600°C and supplied to the reforming reactor.
상기와 같은 열교환에 의한 승온에 의하여 원료 물질 내에 포함된 원료 수분은 액상과 기상의 2개의 상으로 분리된 상태로 개질반응기에 유입되지 않고, 충분히 기화된 증기 상태의 단일상을 유지하면서 개질반응기에 도입되어 개질촉매에 최적반응조건을 제공할 수 있도록 설계되었다.The moisture of the raw material contained in the raw material by the heating by heat exchange as described above does not flow into the reforming reactor in a state separated into two phases of a liquid phase and a gaseous phase. It was introduced and designed to provide optimum reaction conditions for the reforming catalyst.
이 때, 개질반응기로 공급되는 원료수증기의 양은 수증기 대 탄소 몰비 (S/C: Steam to Carbon molar ratio) 1:2.5~4.0의 비율로 혼합되는 것이 바람직하며, 여기서 S/C 비율이 2.5미만이 되면, 수증기부족으로 개질촉매가 탄소에 의해 피독되어 성능이 저하되는 문제가 있고, 4.0을 초과하면 과량의 수증기 주입으로 열효율이 저하되는 문제가 있기 때문에 바람직하지 않다.At this time, the amount of raw material steam supplied to the reforming reactor is preferably mixed in a ratio of steam to carbon molar ratio (S/C) 1:2.5 to 4.0, where the S/C ratio is less than 2.5. In this case, the reforming catalyst is poisoned by carbon due to insufficient water vapor, resulting in deterioration of performance. If it exceeds 4.0, it is not preferable because there is a problem in that thermal efficiency is lowered due to excessive injection of water vapor.
상기 개질반응기는 상기 혼합물을 개질 촉매에 접촉시키고 수증기 개질하는 것으로, 고농도 수소 함유 가스를 제조한다. 상기 개질반응기의 하부에는 개질반응기를 바깥쪽으로부터 가열하는 버너가 마련되어 있다. In the reforming reactor, the mixture is brought into contact with a reforming catalyst and steam reformed to produce a gas containing a high concentration of hydrogen. A burner for heating the reforming reactor from the outside is provided below the reforming reactor.
상기 개질반응기는 상기 혼합물이 유동 가능하도록 충진한 촉매를 포함하며, 상기 충진된 촉매는 루테늄(ruthenium) 또는 니켈을 알루미나(alumina) 또는 실리카(silica) 담체에 담지시킨 것이 바람직하다.The reforming reactor includes a catalyst filled to allow the mixture to flow, and the filled catalyst is preferably ruthenium or nickel supported on an alumina or silica carrier.
상기 개질반응기에서의 탄화수소의 수증기 개질이 다음의 반응으로 행하여진다.Steam reforming of hydrocarbons in the reforming reactor is carried out in the following reaction.
C mH n + mH 2O → mCO + (m+n/2)H 2 C m H n + mH 2 O → mCO + (m+n/2)H 2
CO + 3H 2 ↔ CH 4 + H 2OCO + 3H 2 ↔ CH 4 + H 2 O
CO + H 2O ↔ CO 2 + H 2 CO + H 2 O ↔ CO 2 + H 2
개질반응기는 버너에 의하여 가열 승온되며, 촉매 반응에 필요한 반응열을 공급하기 위하여 운전 온도를 700∼850℃로 유지한다. The reforming reactor is heated and heated by a burner, and the operating temperature is maintained at 700 to 850°C in order to supply the reaction heat required for the catalytic reaction.
상기 개질반응기를 가열하고 배출된 배기 가스의 온도는 600∼700℃로 열교환기 4에 도입되고, 상기 개질 반응을 통하여 변환된 개질가스(CO, CO 2, CH 4, H 2)는 500∼600℃의 온도로 열교환기 1 내지 3을 거쳐 수성가스반응기에 도입된다.The temperature of the exhaust gas discharged by heating the reforming reactor is 600 to 700°C, and is introduced into the heat exchanger 4, and the reforming gas (CO, CO 2 , CH 4 , H 2 ) converted through the reforming reaction is 500 to 600 It is introduced into the water gas reactor through heat exchangers 1 to 3 at a temperature of °C.
상기 개질가스는, 열교환기 1에서 개질반응기의 원료와 열교환하여 온도를 낮추고, 열교환기 2를 거쳐 수소탈황기 원료에 열을 공급한 후에, 열교환기 3에서 버너로 공급되는 공기를 예열하여 최종적으로 수성가스반응기에 적합한 온도인 170℃~200℃로 조절된다. 수성가스반응은 열역학적으로 온도가 낮을수록 좋으나, 너무 낮을 경우 반응속도가 느려 진다. 따라서 170℃~200℃에서 개질가스가 수성가스반응기에서 반응이 개시되도록 한다. The reformed gas is heat-exchanged with the raw material of the reforming reactor in heat exchanger 1 to lower the temperature, and after supplying heat to the hydrogen desulfurizer raw material through heat exchanger 2, the air supplied from heat exchanger 3 to the burner is preheated to finally It is adjusted to 170℃~200℃, which is a suitable temperature for the water gas reactor. The water gas reaction is thermodynamically better as the temperature is lower, but if the temperature is too low, the reaction rate becomes slow. Therefore, the reformed gas is allowed to start reaction in the water gas reactor at 170°C to 200°C.
상기 수성가스반응기에서의 수성가스 전환 반응은 당업계에 알려진 것으로, CO + H 2O ↔ CO 2 + H 2로 이루어진다. 수성가스반응기에는 개질가스 중의 일산화탄소를 이산화탄소 및 수소로 전환시키는 수성가스 전환 촉매가 충전되어 있고, 수성가스 전환 촉매로서는 철-크롬 또는 동-아연계 등의 산화물인 촉매가 바람직하게 사용될 수 있다. The water gas conversion reaction in the water gas reactor is known in the art, and consists of CO + H 2 O ↔ CO 2 + H 2. The water gas reactor is filled with a water gas conversion catalyst for converting carbon monoxide in the reformed gas into carbon dioxide and hydrogen, and as the water gas conversion catalyst, an oxide catalyst such as iron-chromium or copper-zinc system may be preferably used.
수성가스반응은 발열 반응이며 열역학적으로 온도가 낮을수록 좋으므로, 반응기 출구 온도가 265℃ 이하로 조절하도록 한다.The water gas reaction is an exothermic reaction and thermodynamically, the lower the temperature is, the better, so the reactor outlet temperature should be adjusted to 265°C or less.
수성가스반응기에서 생성된 전환가스(Reformate 2)는 냉각수와 열교환기 7에서 열교환되어 PSA 도입에 적합한 온도로 조절된다. 도 1에서 도시된 바와 같이, 수성가스반응기에서 나오는 전환가스는 일반적으로 250~260℃이나, 후단에 연결되어 있는 수소분리 장치인 PSA의 경우 분리효율은 전환가스의 온도가 낮을수록 좋으며 40℃ 이하를 요구하고 있다. 보다 높은 분리효율을 위하여, 통상 열교환기 7을 사용하여 냉각수로 온도를 낮추어 준다. 이 경우, 전환가스가 보유하고 있는 열에너지를 낭비하는 결과를 초래한다.The conversion gas (Reformate 2) generated in the water gas reactor is heat-exchanged with the cooling water in the heat exchanger 7 to be adjusted to a temperature suitable for PSA introduction. As shown in Figure 1, the conversion gas from the water gas reactor is generally 250 ~ 260 ℃, but in the case of the PSA, which is a hydrogen separation device connected to the rear stage, the separation efficiency is better as the temperature of the conversion gas is lower and 40 ℃ or less. Are demanding. For higher separation efficiency, a heat exchanger 7 is usually used to lower the temperature with cooling water. In this case, the heat energy held by the converted gas is wasted.
따라서, 본 발명에서는 2개의 열교환기를 추가로 사용하여 열효율 및 공정의 안정성을 높였다. 열교환기 5를 통하여 개질반응기 버너의 연료로 사용되는 PSA 배가스가 전환가스로부터 일부 열을 회수할 수 있도록 하였다. Therefore, in the present invention, two heat exchangers are additionally used to increase thermal efficiency and process stability. Through heat exchanger 5, the PSA exhaust gas used as fuel for the reformer burner was able to recover some heat from the conversion gas.
또한, 열교환기 6을 통하여 원료 수증기로 사용되는 탈염수가 전환가스로부터 일부의 열을 회수하도록 하였다.In addition, through the heat exchanger 6, demineralized water used as raw material steam was allowed to recover some heat from the conversion gas.
즉, 본 발명의 수소 제조 장치는 수성가스반응기와 열교환기 7의 사이에 열교환기 5를 추가로 포함하여, PSA배가스를 상기 전환가스와 열교환시켜 승온시키는 것이다.That is, the hydrogen production apparatus of the present invention further includes a heat exchanger 5 between the water gas reactor and the heat exchanger 7, and heat-exchanges the PSA exhaust gas with the conversion gas to increase the temperature.
또한, 본 발명의 수소 제조 장치는 상기 탈염수를 전환가스와 열교환시켜 승온시키는 열교환기 6을 추가로 포함하는 것이 보다 바람직하다. 이 경우, 상기 열교환기 6은 열교환기 5와 열교환기 7사이에 배치되는 것이 바람직하다.In addition, it is more preferable that the hydrogen production apparatus of the present invention further includes a heat exchanger 6 for heat-exchanging the demineralized water with a conversion gas to raise the temperature. In this case, the heat exchanger 6 is preferably disposed between the heat exchanger 5 and the heat exchanger 7.
또한, 상기 열교환기 5에서 예열된 PSA배가스는 개질기반응기의 버너에 공급되어 열을 회수할 수 있도록 구성되었다. 개질반응기의 버너로 공급되는 물질은 연료인 천연가스, LPG 등과, 열교환기 3에서 승온된 공기 및 열교환기 5에서 승온된 PSA배가스로 구성된다.In addition, the PSA exhaust gas preheated in the heat exchanger 5 is configured to be supplied to the burner of the reformer reactor to recover heat. The material supplied to the burner of the reforming reactor is composed of natural gas, LPG, etc., which are fuels, air heated in heat exchanger 3, and PSA exhaust gas heated in heat exchanger 5.
PSA(Pressure Swing Adsorption)는 당업계에서 수소 분리를 위하여 일반적으로 채용하고 있는 공정으로, 압력스윙흡착 분리란, 고농도 수소 함유 가스로부터 흡착제에 의하여 수소 이외의 불순한 가스를 흡착 제거하여, 고순도의 수소로 정제하는 방법이다.PSA (Pressure Swing Adsorption) is a process generally adopted in the art for hydrogen separation.Pressure swing adsorption separation means that impure gases other than hydrogen are adsorbed and removed by an adsorbent from a high-concentration hydrogen-containing gas to produce high-purity hydrogen. This is how to purify.
PSA에서 분리된 고순도 수소는 수소저장탱크에 저장되어 사용되거나 저장장치 없이 연결되어 연료전지나 수소전기차를 위한 수소연료로 활용될 수 있으며, PSA로부터의 배가스는 상기 개질반응기의 가열을 위한 버너의 연료로 재활용되어 열효율을 극대화 한다.The high-purity hydrogen separated from the PSA can be stored in a hydrogen storage tank and used or connected without a storage device to be used as hydrogen fuel for fuel cells or hydrogen electric vehicles, and the exhaust gas from the PSA is used as fuel for the burner for heating the reforming reactor. It is recycled to maximize thermal efficiency.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and variations are possible without departing from the technical spirit of the present invention described in the claims. It will be obvious to those of ordinary skill in the field.
본 발명은 스팀 개질에 의한 수소 제조 공정에 있어서 열효율이 극대화되고 탈황 성능이 강화된 수소 제조 장치에 관한 것이다.The present invention relates to a hydrogen production apparatus in which thermal efficiency is maximized and desulfurization performance is enhanced in a hydrogen production process by steam reforming.

Claims (12)

  1. 원료 탄화수소를 수첨탈황시키는 수소탈황기; 상기 수소탈황기로부터 탈황된 탄화수소 원료와 혼합된 원료수분이 도입되고, 버너에 의하여 가열되어 수증기 개질반응이 이루어지는 개질반응기; 상기 개질반응기로부터의 개질 가스에 대하여 일산화탄소의 수성가스 전환 반응을 위한 수성가스반응기; 및 수소 분리를 위한 PSA(압력스윙흡착)를 포함하는 수소 제조 장치로서,Hydrodesulfurization group for hydrodesulfurization of raw hydrocarbons; A reforming reactor in which the raw material moisture mixed with the desulfurized hydrocarbon raw material is introduced from the hydrogen desulfurizer and heated by a burner to perform a steam reforming reaction; A water gas reactor for a water gas conversion reaction of carbon monoxide with respect to the reformed gas from the reforming reactor; And as a hydrogen production apparatus comprising a PSA (pressure swing adsorption) for hydrogen separation,
    상기 탈황된 탄화수소 원료와 혼합시키기 전에 상기 원료수분을 단일 상의 수증기로 과열시키기 위하여, 상기 버너로부터 배출되는 연소배가스와 열교환시키는 열교환기 4;A heat exchanger 4 for exchanging heat with the combustion exhaust gas discharged from the burner in order to overheat the raw material moisture with steam in a single phase before mixing with the desulfurized hydrocarbon raw material;
    상기 탈황된 탄화수소 원료와 상기 과열된 수증기의 혼합물을 상기 개질반응기로부터 배출되는 개질가스와 열교환시켜 개질반응기로 도입시키는 열교환기 1;A heat exchanger 1 for introducing a mixture of the desulfurized hydrocarbon raw material and the superheated steam into a reforming reactor by exchanging heat with the reformed gas discharged from the reforming reactor;
    상기 열교환기 1을 거친 개질가스가 상기 수성가스반응기로 도입되기 전에 감온되도록, 외부 공기와 열교환시키는 열교환기 3;A heat exchanger 3 for exchanging heat with external air so that the reformed gas passing through the heat exchanger 1 is reduced to temperature before being introduced into the water gas reactor;
    상기 수성가스반응기부터 생성된 전환가스가 상기 PSA로 도입되기 전에 감온되도록, 냉각수와 열교환시키는 열교환기 7; 및A heat exchanger 7 for exchanging heat with cooling water so that the converted gas generated from the water gas reactor is reduced to temperature before being introduced into the PSA; And
    탄화수소 원료와 상기 PSA로부터 재순환된 수소의 혼합물을 개질가스와의 열교환으로 승온시키기 위해, 상기 열교환기 1 및 열교환기 3의 사이에 구비된 열교환기 2;를 포함하는 수소 제조 장치.A hydrogen production apparatus comprising: a heat exchanger 2 provided between the heat exchanger 1 and the heat exchanger 3 to raise the temperature of the mixture of the hydrocarbon raw material and the hydrogen recycled from the PSA through heat exchange with the reformed gas.
  2. 제1항에 있어서, 상기 수성가스반응기와 열교환기 7의 사이에 배치되어, 상기 PSA의 배가스를 상기 전환가스와 열교환시켜 승온시키는 열교환기 5를 추가로 포함하는 수소 제조 장치.The hydrogen production apparatus according to claim 1, further comprising a heat exchanger 5 disposed between the water gas reactor and the heat exchanger 7, and heat-exchanging the exhaust gas of the PSA with the conversion gas to increase temperature.
  3. 제1항에 있어서, 상기 원료수분을 전환가스와 열교환시켜 승온시키는 열교환기 6이 열교환기 7을 대체하거나 추가로 포함되는 수소 제조 장치.The hydrogen production apparatus according to claim 1, wherein a heat exchanger 6 for heat-exchanging the raw material moisture with a conversion gas to increase temperature is substituted or additionally included in the heat exchanger 7.
  4. 제3항에 있어서, 상기 열교환기 6이 열교환기 5와 열교환기 7의 사이에 배치되는 수소 제조 장치.The hydrogen production apparatus according to claim 3, wherein the heat exchanger 6 is disposed between the heat exchanger 5 and the heat exchanger 7.
  5. 제1항에 있어서, 상기 탄화수소 원료의 일부, 상기 열교환기 3에서 승온된 공기, 및 상기 PSA의 배가스가 상기 버너에 공급되는 수소 제조 장치.The hydrogen production apparatus according to claim 1, wherein a part of the hydrocarbon raw material, air heated in the heat exchanger 3, and exhaust gas of the PSA are supplied to the burner.
  6. 제5항에 있어서, 상기 PSA의 배가스가 상기 수성가스반응기와 열교환기 7의 사이에 배치된 열교환기 5에 의해 승온되는 수소 제조 장치.The hydrogen production apparatus according to claim 5, wherein the exhaust gas of the PSA is heated by a heat exchanger 5 disposed between the water gas reactor and heat exchanger 7.
  7. 제1항 내지 제3항 중 어느 한 항에 있어서, 상기 열교환기 1 내지 7은 핀 튜브 형태(Finned tube) 열교환기, 판상 열교환기(Plate type heat exchanger), 멀티튜브 헤어핀 형(Multitube hairpin type) 또는 셀 앤드 튜브 형태(Shell and tube type)의 열교환기인 수소 제조 장치.The method of any one of claims 1 to 3, wherein the heat exchangers 1 to 7 are finned tube heat exchangers, plate type heat exchangers, and multitube hairpin types. Or a hydrogen production device that is a heat exchanger of a shell and tube type.
  8. 제1항에 있어서, 상기 탄화수소 원료는 천연가스, LPG 및 나프타(Naphtha)를 하나 이상 포함한 기상 또는 액상 탄화수소인 수소 제조 장치.The apparatus of claim 1, wherein the hydrocarbon raw material is a gaseous or liquid hydrocarbon containing at least one natural gas, LPG, and Naphtha.
  9. 제1항에 있어서, 상기 개질반응기는 상기 혼합물이 유동 가능하도록 촉매를 충진한 촉매 반응부를 포함하며,The method of claim 1, wherein the reforming reactor comprises a catalytic reaction unit filled with a catalyst to allow the mixture to flow,
    상기 촉매 반응부에 충진된 촉매는 루테늄(ruthenium) 또는 니켈을 알루미나(alumina) 또는 실리카(silica) 담체에 담지시킨 것인 수소 제조 장치.The catalyst filled in the catalytic reaction unit is a hydrogen production apparatus in which ruthenium or nickel is supported on an alumina or silica support.
  10. 제1항에 있어서, 상기 수소탈황기내의 촉매는 코발트, 아연, 동, 몰리브덴 및 니켈로부터 선택된 하나 이상의 금속이나 금속산화물 또는 유화물; 제오라이트; 또는 활성탄을 포함하는 수소 제조 장치.According to claim 1, The catalyst in the hydrogen desulfurization group is at least one metal selected from cobalt, zinc, copper, molybdenum and nickel, metal oxides or emulsions; Zeolite; Or an apparatus for producing hydrogen containing activated carbon.
  11. 제1항에 있어서, 상기 개질반응기로 공급되는 원료수증기의 양은 수증기 대 탄소 몰비가 1:2.5~4.0의 비율로 혼합되는 수소 제조 장치.The hydrogen production apparatus according to claim 1, wherein the amount of raw material steam supplied to the reforming reactor is mixed in a ratio of 1:2.5 to 4.0 in a molar ratio of steam to carbon.
  12. 제1항에 있어서, 상기 수성가스반응기내의 촉매는 철-크롬계 촉매 또는 동-아연계 촉매인 수소 제조 장치.The hydrogen production apparatus according to claim 1, wherein the catalyst in the water gas reactor is an iron-chromium-based catalyst or a copper-zinc catalyst.
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