201103863 六、發明說明： 【發明所屬之技術領域】 置與方 而可 及富氫氣體製造與 法 本創作係-種關於富氫氣體與 ，尤指反應器的結構設計，利用u 眾以之堂σ裒』 ®很、隹—> 名減制、萤蚀用加熱几件與閥件的調控， 卓獨進行#虱氣體製造、早獨純氫氣體製、生、 氫氣純化之整合反應。 & 【先前技術】 按，能源的消耗與國家經濟& i Ba 國家往往能源的消耗也越大。自從 係極為密切，通常越開發 油禁運事件及伊朗革命（史稱為宽—73年及1979年各別發生石 來，替代燃料的開發及能源的有效故久與第二次能源危機）以 的課題。 双g理已成為各國工業發展重要 雖然傳統性化石燃料如煤、石 能源供給的主要祕，但根據然氣仍為世界各國日後 數字顯示，全球石油Μ量約可維心年^國石油公司發表之統計 煤炭則可維持122年。隨著石油與天^吏用量'天'然氣約60年、 源利用（火力發電）仍伴隨著嚴的曰漸稀少，目前煤炭能 t ^ςπ @ 重的裱境污染問題（如煤灰、硫 氧化物S〇x、氮乳化物NOx友重合屬知 Μ ^ ^ ^ ^ _ 金屬之排放）’且鈾礦發電及核廢 料處理廣受環保人士的批評，因此 挑戰。 因此未來能源使用可能面臨嚴峻的 除了前述能源供應間題外，由於全球工t發展及人類活動大 量排放空氣污染物及溫室氣體（如二氧化碳），促使大氣溫室效應 及全球溫暖化現象日趨嚴重。以台灣為例，目前二氧化碳總排放 ，約佔全球總量1%，全球排名第22;自1990年起溫室氣體的排放 量每年成長約5%，且自1998年後’二氧化碳的總排放量仍迅速攀 升’並預估至2020年二氧化碳的總排放量，將由1990年的121百萬 公噸提升至461百萬公噸，成長約3.81倍。另一方面，過去百年以 201103863 t 來，全球平均增溫約為0.6°C，台灣平均增溫則約為1.4°C，遠高於 全球平均增溫幅度，因此節能減碳行動及綠色能源開發刻不容緩。 在眾多能源發展策略中，由於全球體認到氫氣的利用能夠減 少對石油進口的依賴，同時能降低空氣污染物及溫室氣體的排 放，因而在未來數十年極具潛力。若和再生能源如太陽能及風能 比較，上述再生能源往往受限地理環境或氣象等因素而無法持續 供應，氫能則可加以儲存以供不時之需，同時可運輸到任何需要 之處，若以此特性論之，氫氣可視為「能源載體」。 事實上，過去以來氫燃料的運用在工業界向來重要，此係因 氫氣來源豐富、用途廣泛、且運用過程無污染或低污染之故。在 ® 來源方面，生產氫氣的主要原料可為水、生質物及化石燃料；在 用途方面，氫氣過去以來就是化工業的重要原料，例如製氨或肥 料工業、甲醇合成、煤液化過程之除硫、液態燃料脫硫、石油精 鍊（或輕油裂解）、半導體之精製、製鐵、冶金乃至食品工業等； 至於運用過程，以氫氣做為燃料用於内燃機、氣渦輪機及燃料電 池等，發電過程幾乎無污染，且主要產物為水，在環境中可循環， 因此氫氣運用及氫能開發甚具環境友善性。 整體而言，氫能經濟的開發涉及多個層面，主要包含氫氣的 生產、運輸、儲存、轉換及末端使用等。不論是生產、輸送、儲 ® 存、轉換或末端使用，其皆需要完整的氫能基礎設施為骨幹。由 上综而觀之，可知氫氣的生產是氫能經濟建立的首要步驟，而且 未來若氫能經濟急速發展，可預期氫氣的生產將日益重要。 一般而言，氫氣的生產係先製造出富氫氣體，而後依工業用 途及氫氣純度需求，進行氫氣分離及純化程序。例如甲醇合成所 需之氫氣濃度較低；反之，質子交換膜燃料電池所需的氫氣純度 甚高。因此，富氫氣體的產生及純氫的製造，甚至兩者的整合， 是未來氫能經濟建立極重要的一環。 201103863 : 【發明内容】 有鑑於上述需求，發明人乃研究出一種「富氫與純氫氣體製 造之整合裝置與方法（Integrated device and method for producing hydrogen-rich and pure hydrogen gases)」，該裝置及方法除可單 獨進行富氫氣體的製造或單獨進行氫氣的分離及純化外，也可進 行富氫氣體製造與氫氣純化的整合反應。因此，充分依據實際工 業對氫氣之需求，開發出一種可調整式反應器，進行富氫與純氫 氣體的製造。 為了達成上述目的之技術内容，係提供一種「富氫與純氫氣 φ 體製造之整合裝置」，其包含一進料單元、一預熱單元、兩段式 反應單元、一氫氣分離與純化單元及一氣體分析單元，各段反應 單元與氫氣純化單元間的流道皆裝有閥件。當反應物進入該整合 裝置並反應後，藉由閥件的控制，可單獨進行富氫氣體製造、單 獨純氫氣體製造、及富氫氣體製造與氫氣分離純化之整合反應。 所產生的富氫氣體可直接做為燃料，產氣也可為合成氣以應用於 化工業，而分離及純化後的氫氣則可應用於氣體業、化工業及作 為低溫燃料電池的燃料。 【實施方式】201103863 VI. Description of the invention: [Technical field to which the invention belongs] The production of hydrogen-rich gas and the creation of the law-based system - the design of hydrogen-rich gas and, in particular, the reactor, the use of u σ裒』 ® is very, 隹 -> 〗 〖Reducing the number, heating and control of the valve and the control of the valve, Zhuo Duo #虱 gas production, early pure hydrogen system, raw, hydrogen purification integration reaction. & [Prior Art] According to, energy consumption and national economy & i Ba countries tend to consume more energy. Since the system is extremely close, it has generally developed the oil embargo and the Iranian revolution (historically known as the wide-73 and 1979 stone, the development of alternative fuels and the effective energy and the second energy crisis) Question. Double g has become an important part of industrial development in various countries. Although the main secret of traditional fossil fuels such as coal and stone energy supply, according to the future, the number of countries around the world shows that the global oil quantity is about the year of the United States. The statistical coal can last for 122 years. With the use of oil and gas, the amount of 'day' is about 60 years, and the source utilization (thermal power generation) is still accompanied by strict enthalpy. At present, coal can be t ^ ς π @ heavy environmental pollution problems (such as coal ash, Sulphur oxides S〇x, nitrogen emulsifiers, NOx, are known as ^ ^ ^ ^ _ metal emissions) and uranium power generation and nuclear waste disposal are widely criticized by environmentalists and therefore challenged. Therefore, the future energy use may face severe problems. In addition to the aforementioned energy supply issues, due to the global development of labor and human activities, a large number of air pollutants and greenhouse gases (such as carbon dioxide) have contributed to the increasing atmospheric greenhouse effect and global warming. Take Taiwan as an example, the current total carbon dioxide emissions account for about 1% of the global total, ranking 22nd in the world; since 1990, greenhouse gas emissions have grown by about 5% each year, and since 1998, the total emissions of carbon dioxide are still The rapid increase in 'and the estimated total carbon dioxide emissions by 2020 will increase from 121 million metric tons in 1990 to 461 million metric tons, an increase of about 3.81 times. On the other hand, in the past 100 years, with 201103863 t, the global average temperature increase is about 0.6 °C, and the average temperature increase in Taiwan is about 1.4 °C, which is much higher than the global average temperature increase. Therefore, energy conservation and carbon reduction actions and green energy development There is no time to delay. Among the many energy development strategies, the global recognition that hydrogen utilization can reduce dependence on oil imports, while reducing air pollutants and greenhouse gas emissions, has great potential in the coming decades. If compared with renewable energy sources such as solar energy and wind energy, the above-mentioned renewable energy sources are often limited by geographical environment or meteorological factors and cannot be continuously supplied. Hydrogen energy can be stored for emergency use and transported to any need. According to this characteristic, hydrogen can be regarded as an "energy carrier." In fact, the use of hydrogen fuel has always been important in the industry because of its rich source of hydrogen, its versatility, and its use without pollution or low pollution. In terms of source, the main raw materials for hydrogen production can be water, biomass and fossil fuels. In terms of use, hydrogen has been an important raw material for the chemical industry in the past, such as ammonia production or fertilizer industry, methanol synthesis, and sulfur removal in coal liquefaction process. , liquid fuel desulfurization, petroleum refining (or light oil cracking), semiconductor refining, iron making, metallurgy and even food industry; as for the application process, using hydrogen as fuel for internal combustion engines, gas turbines and fuel cells, etc., power generation process It is almost pollution-free and the main product is water, which can be recycled in the environment. Therefore, hydrogen utilization and hydrogen energy development are environmentally friendly. Overall, the development of hydrogen energy economy involves multiple levels, including hydrogen production, transportation, storage, conversion and end use. Whether it is production, transportation, storage, conversion, or end use, it requires a complete hydrogen energy infrastructure as the backbone. From the above, it can be seen that the production of hydrogen is the first step in the establishment of hydrogen energy economy, and in the future, if the hydrogen energy economy develops rapidly, it is expected that hydrogen production will become increasingly important. In general, hydrogen production is the first to produce a hydrogen-rich gas, and then the hydrogen separation and purification process is carried out according to industrial use and hydrogen purity requirements. For example, the concentration of hydrogen required for methanol synthesis is low; conversely, the purity of hydrogen required for a proton exchange membrane fuel cell is very high. Therefore, the production of hydrogen-rich gas and the manufacture of pure hydrogen, and even the integration of the two, is an extremely important part of the future hydrogen energy economy. In the light of the above-mentioned needs, the inventors have developed a "integrated device and method for producing hydrogen-rich and pure hydrogen gases", The method can also carry out the integration reaction of hydrogen-rich gas production and hydrogen purification, in addition to the production of hydrogen-rich gas alone or the separation and purification of hydrogen alone. Therefore, based on the actual industrial demand for hydrogen, an adjustable reactor was developed to produce hydrogen-rich and pure hydrogen gas. In order to achieve the technical object of the above object, an "integrated device for manufacturing hydrogen-rich and pure hydrogen gas" is provided, which comprises a feed unit, a preheating unit, a two-stage reaction unit, a hydrogen separation and purification unit, and A gas analysis unit, the flow path between each reaction unit and the hydrogen purification unit is equipped with a valve member. After the reactants enter the integrated apparatus and react, the integrated reaction of hydrogen-rich gas production, single pure hydrogen gas production, and hydrogen-rich gas production and hydrogen separation and purification can be separately performed by the control of the valve member. The hydrogen-rich gas produced can be directly used as a fuel, and the gas produced can also be a synthesis gas for use in the chemical industry, and the separated and purified hydrogen can be used in the gas industry, the chemical industry, and as a fuel for low-temperature fuel cells. [Embodiment]
本發明裝置是以如®1所示之富氫與純氫氣體製造之整合裝 置作為優選的實施例結構，其不但可依據工業實際需求 氣體的製造’也可將所產生的富氫氣體進-步處理，以製造高純 度的氫氣，該富氫與純氫氣體製造之整合裝置⑴包括： -進料早7L(1G) ’具有液體儲槽（11)、泵（12)、氣體健 及導管三14) ’液體槽⑼可儲存液態碳氮化合物或水並以 傳送，祕儲槽（13)内可置敌反應氣體或攜帶氣體反應物或 氣體將經由導管（14)流人後續之難單sA攜帶 預熱單70(20) ’具有預熱管（21)、加熱器（22)及蓄熱介質 201103863 • (23)，預熱管（21)外包覆有加熱器（22)，預熱管（21)内則充填有蓄 熱介質（23)，加熱器（22)連接有溫度控制裝置，以控制反應物及攜 帶氣體的預熱溫度，而後反應物及攜帶氣體將經由導管及控制閥 一（2句的控制流入後續之反應單元； 兩段式反應單元（30)，具有反應器一（31)及反應器二(32)，兩 座反應器外皆包覆有加熱器（33)，内部則充填有觸媒（34)，以觸發 化學反應產生富氫氣體’反應器一（31)及反應器二(32)間裝設有控 制閥二(35)，其可控制反應單元為一段式或兩段式反應； 一氫氣分離與純化單元(40)，具有控制閥三(41)及控制閥四 (42) ’其後各自連接分離器一（43)及分離器二(44)，兩座分離器内 • 皆裝設有薄膜管(45) ’薄膜管表面可覆有一層鈀薄膜，兩座分離器 藉由控制閥三(41)及控制閥四（42)的操作，可直接將生產的富氫氣 體(46)釋放至反應裝置外，或將富氫氣體引入兩座分離器中進一步 分離及純化氫氣(47)’兩座分離器外也包覆有加熱器，其可控制薄 膜管的溫度以分離及純化氮氣； 一氣體分析單元(50)，具有背壓閥一（51)及背壓閥二(52)，其 可控制兩座反應器及兩座分離器的壓力，兩座背壓閥後連接氣相 層析儀（53)及氣體分析儀（54)，氣相層析儀（53)可分析純化氫氣 (46)、尾氣(55)或富氫氣體(46)内的氫氣濃度，氣體分析儀(54)則可 春分析富氫氣體(46)或尾氣（55)内的一氧化碳、二氧化碳及甲烷濃 度。 本發明方法的技術内容，請配合參看圖2所示，首先啟動液 體泵（12)，使液體自液體儲槽（11)經由導管（14)進入預熱管（21)中， 同時打開氣體儲槽（13)，使氣體以固定流量的方式流入預熱管(21) 中’液體在預熱管(21)内受熱後將轉變成氣相並與氣體均勻混合。 調整控制閥一（24)，若使混合氣直接進入反應器二（32)，將使混合 氣進行一段式反應以產生富氫氣體(46);若使混合氣進入反應器一 (31)，開啟控制閥二(35)且關閉控制閥三（41)，並使混合氣進入反 應器二(32) ’則可使混合氣進行兩段式反應以產生富氫氣體(46)。 201103863 • 調整控制閥三(41)，可直接收集一段式反應所產生的富氫氣體(46) 或將富氫氣體導入分離器一（43)進行氫氣分離與純化；關閉控制閥 三(41)並調整控制閥四（42)，可直接收集兩段式反應所產生的富氮 氣體(46)或將富氫氣體導入分離器二(4句進行氫氣分離與純化。背 壓閥二（52)關閉時’兩座反應器及分離器内的壓力乃由背壓閥一 (51)所控制；若背壓閥一（51)關閉時’兩座反應器及分離器内的壓 力則由背壓閥二(52)所控制。分離後的純化氫氣(47)可由氣相層析 儀(53)進行純度分析’殘餘的尾氣(55)則可由氣體分析儀（54)及氣 相層析儀（53)進行一氧化碳(c〇)、二氧化碳((：〇2)、氫氣(Ho及曱 燒(CH4)之濃度分析，以得知並評估薄膜管對氫氣分離及純化的效 • 果。 本發明可藉由以下實施例被進一步瞭解，該實施例僅做為說 明之用，而非用於限制本發明範圍。 實施例1 在實施例1中乃以本富氫與純氫氣體製造之整合裝置進行高 溫及低溫水氣轉移串聯反應，藉由蒸汽與合成氣反應以產生富氫 氣體’進而以分離器獲得純氫。在操作參數方面，水的進料量固 定為0.5 cc/min、合成氣中氫氣與一氧化碳比例為丨：卜預熱管溫 度設定為30〇。〇反應器一内部填充顆粒狀高溫水氣轉移觸媒且溫 • 度設定為500°C、反應器二内部填充顆粒狀低溫水氣轉移觸媒且溫 度設定為200。〇分離器溫度設定為35〇。(：、控制閥三及背壓閥一 關閉、其餘控制閥閥為開啟狀態，且調整背壓閥二使反應器及分 離器内錶屋力為1〇 atR1，藉由調整合成氣流量，可控制反應物裡 蒸汽與一氧化碳體積流率與比值〃 配合參看圖3與圖4,圖形所得結果為在本發明整合裝置運轉 及上述操作條件下，兩段式水氣轉移反應及富氫氣體通過分離器 後純氫與一氧化碳之濃度分佈圖，其中整合裝置所控制的蒸汽與 一氧化碳比值（S/C)範圍介於1至6之間。由圖3可看出，當蒸汽 201103863 : 與一氧化碳比值較低時，純氫濃度較高，隨著蒸汽與一氧化碳比 值的增加’純氫濃度則略為下降。具體而言，當S/C=i時，純氫 濃度高達99.9931%，而當S/C=6時，純氫濃度則為99,9728%，雖 然純氫濃度略為下降，但氫氣純度仍然甚高。至於圖4 一氧化碳 濃度分佈圖則顯示，當S/C-1時，純氫中一氧化碳j農度僅有Μ ppm，當S/C=6時，氫氣中一氧化碳濃度則有52 ppm。由於產生 的氫氣中一氧化碳濃度極低’因此本整合裝置所產生的氫氣可應 用於低溫燃料電池’如質子交換骐燃料電池。此外，分析中也顯 示，合成氣經兩段式水氣轉移反應後，一氧化碳轉化率皆高達93% 以上。 φ 另外’為說明本整合裝置可用於生產富氫氣體，圖5為僅使 用單段反應且無使用分離器，個別進行高溫水氣轉移反應及低溫 水氣轉移反應所產生之畐氫氣體成分，其中操作參數同圖3與圖4 之控制。由圖5所得結果可看出，單獨進行高溫水氣轉移反應時， 產氣中虱氣濃度可達65.91/ί> ’合成氣中一氧化碳的轉化率則可達 90.48%。至於單獨使用低溫水氣轉移反應，產氣中氫氣濃度則可 達67.43%，一氧化碳轉化率可高達99.94%。 實施例2 在實施例2則以本富氫與純氫氣體製造之整合裝置進行甲醇 籲蒸汽重組及低溫水氣轉移串聯反應以產生富氫氣體，進而以分離 器獲得純氫。在操作參數方面，曱醇與水以體積2: 3之方式先行 混合，而後以0.3 cc/min的體積流率送至進料單元。在此同時，氮 氣以910-1050 cc/min的體積流率送至進料元件，氮氣作用乃作為 攜帶氣體，以協助甲醇與水在反應管的流動。預熱管溫度設定為 300°C、反應器一内部填充顆粒狀蒸汽重組觸媒且溫度設定為 200°C至350°C之間、反應器二内部填充顆粒狀低溫水氣轉移觸 媒且溫度設定為200。(：、分離器溫度設定為350°C，另外，調整背 壓閥二使反應器及分離器内錶壓力為7.5atm，。 201103863 配合參看圖6及圖7,其為在上述操作條件及本發明之整合裝 置運轉下，曱醇與水經蒸汽重組、低溫水氣轉移反應及氫氣分離 後，甲醇轉化率及氫氣回收率隨蒸汽重組溫度變化之分佈圖。圖 中可看出當蒸汽重組溫度為200°C時，甲醇轉化率約為73.8%， 而氫氣回收率則僅有36.4%。隨著重組溫度的上升，甲醇轉化率也 跟著上升，當重組溫度達350°C時，曱醇轉化率已高達95%，至 於氫氣回收率則上升至68.2%。圖8另顯示在不同重組溫度下，富 氫氣體經分離管處理純氫之濃度分佈。整體而言，氫氣濃度至少 可達99.93%以上。以上結果說明在本創作裝置作用下，也可進行 蒸汽重組結合水氣轉移反應，以將甲醇與水反應，進而產生富氫 氣體及高純度氫氣。 綜上所述，本發明「富氫與純氫氣體製造之整合裝置與方法」， 藉由自行設計及架設之整合裝置，若無任何化學反應，本整合裝 置可單獨進行氣體中氫氣的分離與純化，若在觸媒作用下，反應 器内可以激發各種碳氫化合物及水反應，因而生產富氫氣體，若 將富氫氣體流經分離器，則可進一步生產高純度氫氣，因此本整 合裝置具有多重用途，可依據工業的各種需求，以不同方法操作 本裝置以產生富氫氣體及純氫，亦即，本發明方法係利用自然法 • 則技術思想之高度創作，符合發明專利要件，爰依法俱文提出申 請。 【圖式簡單說明】 圖1為本發明之富氫與純氫氣體製造整合裝置示意圖（代表圖）。 圖2為本發明方法之富氫與純氫氣體製造流程圖。 圖3為實施本發明設備，合成氣經兩段式水氣轉移反應及富氫氣 體通過分離器後氫氣之濃度分佈圖 圖4為實施本發明設備，合成氣經兩段式水氣轉移反應及富氫氣 體通過分離器後一氧化碳之濃度分佈圖 201103863 圖5為實施本發明設備，合成氣個別進行高溫水氣轉移反應及低 溫水氣轉移反應所產生之富氫氣體成分。 圖6為實施本發明設備，曱醇經蒸汽重組、低溫水氣轉移反應及 富氫氣體通過分離器後曱醇轉化率分佈圖。 圖7為實施本發明設備，甲醇經蒸汽重組、低溫水氣轉移反應及 富氫氣體通過分離器後氫氣回收率分佈圖。 圖8為實施本發明設備，曱醇經蒸汽重組、低溫水氣轉移反應及 富氫氣體通過分離器後氫氣濃度分佈圖。 【主要元件符號說明】The device of the present invention is an integrated device made of a hydrogen-rich and pure hydrogen gas as shown in ®1 as a preferred embodiment structure, which can not only manufacture the gas according to the actual industrial demand, but also can generate the hydrogen-rich gas generated. Step processing to produce high-purity hydrogen, the integrated device for manufacturing hydrogen-rich and pure hydrogen gas (1) includes: - 7L (1G) as early as feed - with liquid storage tank (11), pump (12), gas and conduit 3)) 'Liquid tank (9) can store liquid carbon-nitrogen compounds or water for transport, and the enemy reaction gas or carrier gas reactant or gas in the secret storage tank (13) will flow through the conduit (14). sA carries preheating sheet 70(20) 'with preheating tube (21), heater (22) and heat storage medium 201103863 • (23), preheating tube (21) is covered with heater (22), preheating The tube (21) is filled with a heat storage medium (23), and the heater (22) is connected with a temperature control device for controlling the preheating temperature of the reactant and the carrier gas, and then the reactant and the carrier gas are passed through the conduit and the control valve. (The control of 2 sentences flows into the subsequent reaction unit; the two-stage reaction unit 30), having a reactor one (31) and a reactor two (32), both reactors are covered with a heater (33), and the inside is filled with a catalyst (34) to trigger a chemical reaction to generate hydrogen-rich A control valve 2 (35) is arranged between the gas 'reactor one (31) and the second reactor (32), which can control the reaction unit to be a one-stage or two-stage reaction; a hydrogen separation and purification unit (40), The control valve three (41) and the control valve four (42) are respectively connected to the separator one (43) and the separator two (44), and both of the separators are provided with a thin film tube (45) 'film The surface of the tube may be covered with a palladium film, and the two separators can directly release the produced hydrogen-rich gas (46) to the outside of the reaction device by the operation of the control valve three (41) and the control valve four (42), or The hydrogen-rich gas is introduced into the two separators to further separate and purify the hydrogen (47). The two separators are also coated with a heater, which can control the temperature of the thin film tube to separate and purify the nitrogen; a gas analysis unit (50) , with back pressure valve one (51) and back pressure valve two (52), which can control the pressure of two reactors and two separators, two backs The gas chromatograph (53) and the gas analyzer (54) are connected to the valve, and the gas chromatograph (53) can analyze the hydrogen concentration in the purified hydrogen (46), exhaust gas (55) or hydrogen-rich gas (46). The gas analyzer (54) can analyze the concentration of carbon monoxide, carbon dioxide and methane in the hydrogen-rich gas (46) or the exhaust gas (55) in spring. The technical content of the method of the invention, please refer to FIG. 2, first start the liquid pump (12), let the liquid enter the preheating pipe (21) from the liquid storage tank (11) via the conduit (14), and simultaneously open the gas storage tank (13), so that the gas flows into the preheating pipe (21) at a fixed flow rate. The liquid in the liquid in the preheating tube (21) will be converted into a gas phase and uniformly mixed with the gas. Adjusting the control valve one (24), if the mixed gas directly enters the reactor two (32), the mixed gas is subjected to a one-stage reaction to generate a hydrogen-rich gas (46); if the mixed gas is introduced into the reactor one (31), Opening control valve two (35) and closing control valve three (41) and passing the mixture into reactor two (32)' allows the mixture to undergo a two-stage reaction to produce a hydrogen rich gas (46). 201103863 • Adjust the control valve three (41) to directly collect the hydrogen-rich gas (46) produced by the one-stage reaction or introduce the hydrogen-rich gas into the separator one (43) for hydrogen separation and purification; close the control valve three (41) And adjust the control valve four (42), can directly collect the nitrogen-rich gas (46) produced by the two-stage reaction or introduce the hydrogen-rich gas into the separator two (4 sentences for hydrogen separation and purification. Back pressure valve two (52) When closed, the pressure in the two reactors and the separator is controlled by the back pressure valve (51); if the back pressure valve (51) is closed, the pressure in the two reactors and the separator is back pressure. Controlled by valve two (52). The purified hydrogen (47) after separation can be purified by gas chromatograph (53). 'Residual exhaust gas (55) can be analyzed by gas analyzer (54) and gas chromatograph ( 53) Carrying out concentration analysis of carbon monoxide (c〇), carbon dioxide ((:〇2), hydrogen (Ho and calcined (CH4)) to know and evaluate the effect of the thin film tube on hydrogen separation and purification. This embodiment is further understood by the following examples, which are for illustrative purposes only and are not intended to limit the scope of the present invention. Embodiment 1 In Embodiment 1, a high-temperature and low-temperature water gas transfer series reaction is performed by using an integrated device made of hydrogen-rich hydrogen gas and pure hydrogen gas, and steam is reacted with synthesis gas to generate a hydrogen-rich gas, and then obtained by a separator. Pure hydrogen. In terms of operating parameters, the feed rate of water is fixed at 0.5 cc/min, and the ratio of hydrogen to carbon monoxide in the synthesis gas is 丨: the temperature of the preheating tube is set to 30 〇. The inside of the reactor is filled with granular high temperature water. The gas transfer catalyst was set to a temperature of 500 ° C, and the reactor 2 was filled with a particulate low-temperature water gas transfer catalyst and the temperature was set to 200. The temperature of the helium separator was set to 35 〇. (:, control valve three and back When the pressure valve is closed and the remaining control valve is open, and the back pressure valve 2 is adjusted, the internal force of the reactor and the separator is 1 〇 at R1, and the volume of steam and carbon monoxide in the reactant can be controlled by adjusting the flow rate of the synthesis gas. The flow rate and ratio 〃 are combined with reference to Fig. 3 and Fig. 4. The result obtained by the graph is that under the operation of the integrated device of the present invention and the above operating conditions, the two-stage water gas shift reaction and the hydrogen-rich gas pass through the separator after the pure hydrogen and The concentration profile of carbon oxide, wherein the ratio of steam to carbon monoxide (S/C) controlled by the integrated device ranges from 1 to 6. As can be seen from Figure 3, when the ratio of steam 201103863: to carbon monoxide is low, pure The hydrogen concentration is higher, and the pure hydrogen concentration decreases slightly with the increase of the ratio of steam to carbon monoxide. Specifically, when S/C=i, the pure hydrogen concentration is as high as 99.9931%, and when S/C=6, pure The hydrogen concentration is 99,9728%. Although the pure hydrogen concentration is slightly decreased, the hydrogen purity is still very high. As shown in Fig. 4, the carbon monoxide concentration distribution map shows that when S/C-1, the carbon monoxide in pure hydrogen is only the agricultural degree. Μ ppm, when S/C = 6, the concentration of carbon monoxide in hydrogen is 52 ppm. Since the concentration of carbon monoxide in the generated hydrogen gas is extremely low, the hydrogen produced by the integrated device can be applied to a low-temperature fuel cell such as a proton exchange 骐 fuel cell. In addition, the analysis also showed that the conversion rate of carbon monoxide was over 93% after the two-stage water-gas shift reaction of syngas. φ In addition, to illustrate that the integrated device can be used to produce hydrogen-rich gas, Figure 5 shows the composition of the hydrogen gas produced by the high-temperature water-gas shift reaction and the low-temperature water-gas shift reaction using only a single-stage reaction and no separator. The operating parameters are the same as those of Figures 3 and 4. From the results obtained in Figure 5, it can be seen that the concentration of helium in the gas produced can reach 65.91/ί> when the high-temperature water-gas shift reaction is carried out alone. The conversion rate of carbon monoxide in the synthesis gas can reach 90.48%. As for the low-temperature water-gas shift reaction alone, the hydrogen concentration in the gas production can reach 67.43%, and the carbon monoxide conversion rate can be as high as 99.94%. Example 2 In Example 2, an integrated apparatus made of the hydrogen-rich and pure hydrogen gas was used to carry out methanol steam recombination and low-temperature water gas shift series reaction to produce a hydrogen-rich gas, thereby obtaining pure hydrogen as a separator. In terms of operating parameters, decyl alcohol was first mixed with water in a volume of 2:3 and then sent to the feed unit at a volumetric flow rate of 0.3 cc/min. At the same time, nitrogen gas is supplied to the feed element at a volumetric flow rate of 910 to 1050 cc/min, and nitrogen acts as a carrier gas to assist the flow of methanol and water in the reaction tube. The preheating tube temperature is set to 300 ° C, the reactor is internally filled with granular vapor recombination catalyst and the temperature is set between 200 ° C and 350 ° C, and the reactor 2 is filled with granular low temperature water vapor transfer catalyst and temperature. Set to 200. (:, the separator temperature is set to 350 ° C, in addition, adjust the back pressure valve 2 to make the internal pressure of the reactor and separator 7.5 atm. 201103863 with reference to Figure 6 and Figure 7, which is in the above operating conditions and Under the operation of the integrated device of the invention, the distribution of methanol conversion and hydrogen recovery after steam recombination, low-temperature water-gas shift reaction and hydrogen separation, the distribution of methanol conversion rate and hydrogen recovery rate with steam recombination temperature can be seen as the steam recombination temperature. At 200 ° C, the methanol conversion rate is about 73.8%, while the hydrogen recovery rate is only 36.4%. With the increase of the recombination temperature, the methanol conversion rate also increases, when the recombination temperature reaches 350 ° C, the sterol conversion The rate has reached 95%, and the hydrogen recovery rate has risen to 68.2%. Figure 8 also shows the concentration distribution of pure hydrogen treated by a hydrogen-rich gas through a separation tube at different recombination temperatures. Overall, the hydrogen concentration is at least 99.93%. The above results show that under the action of the authoring device, steam recombination combined with water vapor transfer reaction can be carried out to react methanol with water to generate hydrogen-rich gas and high-purity hydrogen gas. Ming "Integrated device and method for hydrogen-rich and pure hydrogen gas production", by means of an integrated device designed and erected by itself, if there is no chemical reaction, the integrated device can separately separate and purify hydrogen in the gas. Under the action, the reactor can excite various hydrocarbons and water to react, thus producing hydrogen-rich gas. If the hydrogen-rich gas flows through the separator, the high-purity hydrogen can be further produced. Therefore, the integrated device has multiple uses and can be based on The various needs of the industry operate the apparatus in different ways to produce hydrogen-rich gas and pure hydrogen. That is, the method of the present invention utilizes the high degree of creation of the natural law and the technical idea of the invention, and conforms to the patent requirements of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view (representative drawing) of a hydrogen-rich and pure hydrogen gas production integration apparatus of the present invention. Figure 2 is a flow chart for manufacturing hydrogen-rich and pure hydrogen gas of the method of the present invention. The concentration distribution of hydrogen in the equipment, synthesis gas after two-stage water-gas shift reaction and hydrogen-rich gas passing through the separator Preparation, synthesis gas after two-stage water-gas shift reaction and hydrogen-rich gas through the separator after carbon monoxide concentration distribution map 201103863 Figure 5 is the implementation of the apparatus of the present invention, synthesis gas gas high temperature water gas transfer reaction and low-temperature water gas transfer reaction The hydrogen-rich gas component produced. Figure 6 is a diagram showing the conversion of sterol conversion after sterol reforming, low-temperature water-gas shift reaction and hydrogen-rich gas passing through a separator in the apparatus of the present invention. Figure 7 is a diagram showing the operation of the apparatus of the present invention, methanol. Hydrogen recovery rate profile after steam recombination, low temperature water gas shift reaction and hydrogen-rich gas passing through the separator. Figure 8 is a diagram showing the operation of the apparatus of the present invention, after sterol recombination by steam, low-temperature water-gas shift reaction and hydrogen-rich gas passing through the separator Hydrogen concentration distribution map. [Main component symbol description]
(1)富氫與純氫氣體製造之整合裝置(1) Integrated device for hydrogen-rich and pure hydrogen gas production
(10) 進料單元 (11) 液體儲槽 （12) (13)氣體儲槽 （14) (20) 預熱單元 (21) 預熱管 （22) (23)蓄熱介質 （24) (30) 兩段式反應單元 (31) 反應器一 (32) (33)加熱器 （34) (35)控制閥二 (40) 氫氣分離與純化單元 (41) 控制閥三 (42) (43)分離器一 （44) (45)薄膜管 （46) (47)純化氫氣 (50) 氣體分析單元 (51) 背壓閥一 (52) (53)氣相層析儀 （54) 泵 導管 加熱器預熱管 控制閥一 反應器二 觸媒 控制閥四 分_器二 富氫氣體 背壓閥二 氣體分析儀 (55)尾氣(10) Feeding unit (11) Liquid storage tank (12) (13) Gas storage tank (14) (20) Preheating unit (21) Preheating pipe (22) (23) Heat storage medium (24) (30) Two-stage reaction unit (31) Reactor one (32) (33) Heater (34) (35) Control valve two (40) Hydrogen separation and purification unit (41) Control valve three (42) (43) separator One (44) (45) Thin film tube (46) (47) Purified hydrogen (50) Gas analysis unit (51) Back pressure valve one (52) (53) Gas chromatograph (54) Pump tube heater preheating Tube control valve-reactor two-catalyst control valve four points _ two hydrogen-rich gas back pressure valve two gas analyzer (55) exhaust