TWI498279B - Manufacturing method of hydrothermal generation of hydrogen and apparatus thereof - Google Patents
Manufacturing method of hydrothermal generation of hydrogen and apparatus thereof Download PDFInfo
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- TWI498279B TWI498279B TW102108706A TW102108706A TWI498279B TW I498279 B TWI498279 B TW I498279B TW 102108706 A TW102108706 A TW 102108706A TW 102108706 A TW102108706 A TW 102108706A TW I498279 B TWI498279 B TW I498279B
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- iron metal
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 75
- 239000001257 hydrogen Substances 0.000 title claims description 58
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000000843 powder Substances 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
本發明係關於一種以水熱法產生氫氣的方法及其裝置，特別是關於一種藉由奈米及微米級鐵金屬粉末與液態水進行反應產生氫氣的方法及其裝置。The present invention relates to a method and apparatus for generating hydrogen by hydrothermal method, and more particularly to a method and apparatus for producing hydrogen by reacting nano and micron-sized iron metal powder with liquid water.
近年來由於油價飆漲，間接的反應出目前石油能源短缺的現象。而石油在燃燒產生能量的時候伴隨著二氧化碳排放，汙染了我們的生活環境，造成溫室效應。在環保意識漸增的當前，各種能夠取代傳統石油的能源被積極開發，其中氫能源正是一個亟待發展的重點。In recent years, due to the soaring oil prices, the indirect reaction to the current shortage of petroleum energy. And when oil is burned to produce energy, it is accompanied by carbon dioxide emissions, polluting our living environment and causing a greenhouse effect. At a time when environmental awareness is increasing, various energy sources that can replace traditional oil are actively developed, and hydrogen energy is a key point for development.
現有商業化的產氫的方法主要分成兩類，一種是以化石原料製氫的方法，包含有：蒸氣重組法、部分氧化法以及水煤氣法。這些方法都需要使用含碳的化石原料，因此在產生氫氣的製程中無可避免的會伴隨二氧化碳廢氣的排放，在大量生產時將會造成環境問題。另一種產氫方法則是使用非化石原料，較常見的是以水為主原料的水電解法。水電解法是一種傳統且成熟的製氫方法，其製造設備僅需要將兩個電極(陰極與陽極)置入電解液中，以直流電通過兩個電極，電解液中的水就會被電解為氫氣與氧氣。雖然水電解法具有製程簡單且無汙染的優點，但因為耗電量高，電費支出一般約佔總生產成本的75~80%，若與化石原料產氫的方法比較之下，較不符合大量生產時的要求，不具有經濟上的競爭力，所以使用水電解法製氫的產量不到全球生產比例的5%。此外，另有一些以水為原料的製氫方法，由於水的能階較低，欲使其分解非常耗能，必須要很高的溫度才能獲得氫氣，因此直接加熱水到3000℃以上使其蒸發為水蒸氣，則水蒸氣會直接分解為氫氣與氧氣，但其操作溫度太高，熱能的供給是一個重大問題。The existing commercial hydrogen production methods are mainly divided into two types, one is a method for producing hydrogen from fossil raw materials, and includes: a steam reforming method, a partial oxidation method, and a water gas method. These methods all require the use of carbon-containing fossil raw materials, so that in the process of generating hydrogen, it is inevitably accompanied by the emission of carbon dioxide exhaust gas, which causes environmental problems in mass production. Another method of hydrogen production is the use of non-fossil raw materials, the more common water electrolysis method using water as the main raw material. The water electrolysis method is a traditional and mature hydrogen production method. The manufacturing equipment only needs to put two electrodes (cathode and anode) into the electrolyte, and direct current through the two electrodes, and the water in the electrolyte is electrolyzed into hydrogen. With oxygen. Although the water electrolysis method has the advantages of simple process and no pollution, because of the high power consumption, the electricity bill generally accounts for 75-80% of the total production cost. If compared with the method of producing hydrogen from fossil raw materials, it is less suitable for mass production. The demand for time is not economically competitive, so the production of hydrogen by water electrolysis is less than 5% of the global production. In addition, there are some water-based hydrogen production methods. Because of the low energy level of water, it is very energy-intensive to decompose. It is necessary to have a high temperature to obtain hydrogen. Therefore, the water is directly heated to above 3000 °C. When evaporated to water vapor, the water vapor will be directly decomposed into hydrogen and oxygen, but the operating temperature is too high, and the supply of heat is a major problem.
故，有必要提供一種產氫方法，以解決習用技術所存在的問題，具有製程簡單、成本低且無汙染的優點，並且能生產純度高的氫氣以便於利用。Therefore, it is necessary to provide a hydrogen production method to solve the problems existing in the conventional technology, and has the advantages of simple process, low cost, and no pollution, and can produce hydrogen with high purity for use.
本發明之主要目的在於提供一種產生氫氣的方法，其係利用加熱液態水至一定溫度，使液態水與鐵粉進行氧化還原反應，製得可直接使用且不須純化的氫氣。The main object of the present invention is to provide a method for producing hydrogen gas by heating liquid water to a certain temperature to carry out a redox reaction between liquid water and iron powder to obtain hydrogen which can be used directly without purification.
本發明之次要目的在於提供一種產生氫氣的方法，其係利用奈米及/或微米級的鐵粉與液態水進行反應，以增加鐵粉與液態水的接觸面積，加快反應進行速率，進而提高製備氫氣效率。A secondary object of the present invention is to provide a method for generating hydrogen by reacting iron and/or micron-sized iron powder with liquid water to increase the contact area between the iron powder and the liquid water, thereby accelerating the reaction rate, and further Improve the efficiency of hydrogen production.
本發明之再一目的在於提供一種成本低廉、製程簡單且易於大量產生氫氣的方法。由於液態水的取得容易且成本較低，因此適合在大量生產的製程中使用，而鐵粉在進行反應後的氧化產物為氧化鐵，其不須經過繁雜處理即可與產物氫氣自然分離，且僅需簡單的表面處理即可還原為鐵金屬，是一種容易回收再次被使用的物質。Still another object of the present invention is to provide a method which is low in cost, simple in process, and easy to generate a large amount of hydrogen. Since liquid water is easy to obtain and low in cost, it is suitable for use in a mass production process, and the oxidation product of the iron powder after the reaction is iron oxide, which can be naturally separated from the product hydrogen without complicated treatment, and It can be reduced to iron metal with a simple surface treatment, and is a substance that is easy to recycle and reused.
為達上述之目的，本發明提供一種以水熱法產生氫氣的方法，其包含步驟：提供一鐵金屬粉末，具有100奈米至10微米的粒徑；提供一液態水；在一密閉容器中混合該鐵金屬粉末及該液態水，形成一混合液；及加熱該混合液至100至200℃，使該鐵金屬粉末及該液態水反應產生氫氣。To achieve the above object, the present invention provides a method for hydrothermally producing hydrogen comprising the steps of: providing an iron metal powder having a particle size of from 100 nm to 10 μm; providing a liquid water; in a closed container Mixing the iron metal powder and the liquid water to form a mixed liquid; and heating the mixed liquid to 100 to 200 ° C to react the iron metal powder with the liquid water to generate hydrogen.
在本發明之一實施例中，該鐵金屬粉末相對於該混合液的重量百分比為10%至30%。In an embodiment of the invention, the weight percentage of the iron metal powder relative to the mixed liquid is from 10% to 30%.
在本發明之一實施例中，加熱該混合液的溫度係介於120至150℃。In one embodiment of the invention, the temperature at which the mixture is heated is between 120 and 150 °C.
在本發明之一實施例中，在混合該鐵金屬粉末及該液態水之前，另包含一表面處理步驟，以去除該鐵金屬粉末的表面雜質及其氧化物。In an embodiment of the invention, before the mixing of the iron metal powder and the liquid water, a surface treatment step is further included to remove surface impurities and oxides thereof.
該表面處理步驟係以稀釋酸液浸泡及清洗該鐵金屬粉末。The surface treatment step is to soak and clean the iron metal powder with a dilute acid solution.
在本發明之一實施例中，該稀釋酸液的體積莫耳濃度大於 0.1M。In an embodiment of the invention, the volumetric molar concentration of the diluted acid solution is greater than 0.1M.
本發明另提供一種以水熱法產生氫氣的反應裝置，其包含：一反應容器，用以容置一鐵金屬粉末及一液態水的一混合液；一加熱裝置，用以加熱該反應容器內之混合液，以反應產生氫氣及水蒸氣的一混合氣體；一冷卻裝置，具有一第一開口部與一第二開口部，該第一開口部與該反應容器之一開口緊密接合，以冷卻該混合氣體；以及一氣體收集筒，與該冷卻裝置之第二開口部緊密接合；其中該冷卻裝置係與地平面夾角90度或以下。The invention further provides a reaction device for generating hydrogen by hydrothermal method, comprising: a reaction vessel for accommodating a mixture of iron metal powder and a liquid water; and a heating device for heating the reaction vessel a mixed liquid for reacting to generate a mixed gas of hydrogen gas and water vapor; a cooling device having a first opening portion and a second opening portion, the first opening portion being tightly coupled to one of the openings of the reaction vessel for cooling The mixed gas; and a gas collecting cylinder that is in close contact with the second opening of the cooling device; wherein the cooling device is at an angle of 90 degrees or less to the ground plane.
在本發明之一實施例中，該冷卻裝置之第一開口部與該反應容器之開口的接合處設置一第一閥門，以控制是否冷卻該混合液加熱所產生的水蒸氣，使得該水蒸氣冷凝回到該反應容器內。In an embodiment of the present invention, a first valve is disposed at a junction of the first opening of the cooling device and the opening of the reaction vessel to control whether to cool the water vapor generated by the heating of the mixed liquid, so that the water vapor Condensation back into the reaction vessel.
在本發明之一實施例中，該冷卻裝置之第二開口部與該氣體收集筒的接合處設置一第二閥門，以控制該氫氣是否流通至該氣體收集筒。In an embodiment of the invention, a second valve is disposed at the junction of the second opening of the cooling device and the gas collection cylinder to control whether the hydrogen gas flows to the gas collection cylinder.
10‧‧‧反應裝置10‧‧‧Reaction device
1‧‧‧反應容器1‧‧‧Reaction vessel
1a‧‧‧開口1a‧‧‧ openings
2‧‧‧加熱裝置2‧‧‧heating device
3‧‧‧冷卻裝置3‧‧‧Cooling device
3a‧‧‧第一開口部3a‧‧‧First opening
3b‧‧‧第二開口部3b‧‧‧second opening
4‧‧‧氣體收集筒4‧‧‧ gas collection cylinder
5a‧‧‧第一閥門5a‧‧‧First valve
5b‧‧‧第二閥門5b‧‧‧second valve
第1圖：本發明二實施例之以水熱法產生氫氣的反應裝置之側視圖。Fig. 1 is a side view of a reaction apparatus for generating hydrogen gas by a hydrothermal method according to a second embodiment of the present invention.
第2圖：本發明探討改變反應所使用的鐵金屬粉末含量重量百分比所造成的生產氫氣的影響曲線圖。Fig. 2: The present invention investigates the effect of hydrogen production on the production of hydrogen by varying the weight percentage of iron metal powder used in the reaction.
第3圖：本發明探討微米級鐵金屬粉末(3微米)在反應溫度改變時的氫氣產量曲線圖。。Figure 3: The present invention investigates the hydrogen production curve of micron-sized iron metal powder (3 microns) as the reaction temperature changes. .
第4圖：本發明探討奈米級鐵金屬粉末(100奈米)在反應溫度改變時的氫氣產量曲線圖。。Figure 4: The present invention investigates the hydrogen production curve of nanoscale iron metal powder (100 nm) as the reaction temperature changes. .
為了讓本發明之上述及其他目的、特徵、優點能更明顯易懂，下文將特舉本發明較佳實施例，並配合所附圖式，作詳細說明如下。再者，本發明所提到的方向用語，例如上、下、頂、底、前、後、左、右、內、外、側面、周圍、中央、水平、橫向、垂直、縱向、軸向、徑向、最上層或最下層等，僅是參考附加圖式的方向。因此，使用的方向用語是用以說明及理解本發明，而非用以限制本發明。The above and other objects, features and advantages of the present invention will become more <RTIgt; Furthermore, the directional terms mentioned in the present invention, such as upper, lower, top, bottom, front, rear, left, right, inner, outer, side, surrounding, central, horizontal, horizontal, vertical, longitudinal, axial, Radial, uppermost or lowermost, etc., only refer to the direction of the additional schema. Therefore, the directional terminology used is for the purpose of illustration and understanding of the invention.
本發明第一實施例中以水熱法產生氫氣的方法主要包含下列步驟：提供一鐵金屬粉末；提供一液態水；在一密閉容器中混合該鐵金屬粉末及該液態水，形成一混合液；及加熱該混合液，使該鐵金屬粉末及該液態水反應產生氫氣。本發明將於下文中詳細說明第一實施例之上述各步驟的實施細節及其原理。The method for generating hydrogen by hydrothermal method in the first embodiment of the present invention mainly comprises the steps of: providing an iron metal powder; providing a liquid water; mixing the iron metal powder and the liquid water in a closed container to form a mixed liquid And heating the mixture to react the iron metal powder with the liquid water to produce hydrogen gas. The details of the implementation of the above-described steps of the first embodiment and the principles thereof will be described in detail below.
在本發明第一實施例之以水熱法產生氫氣的方法中，首先係提供一鐵金屬粉末。在本步驟中，該鐵金屬粉末可為奈米或微米級的粉末，其尺寸大小例如是具有100奈米至10微米的粒徑。隨後，將該鐵金屬粉末以及一液態水置於一密閉容器中加以混合，形成鐵金屬粉末與液態水的混合液。混合的方式不限，可利用攪拌使該混合液較為均勻，或直接靜置亦可。在該鐵金屬粉末與液態水的混合液中，較佳的，使該鐵金屬粉末完全浸入該液態水中，該鐵金屬粉末之重量百分比可介於5%至60%，例如是10%、20%、30%或40%。接著，以加熱裝置加熱該混合液至100℃以上，較佳的是100℃至200℃，可例如為120℃、150℃或180℃。此時，該鐵金屬粉末與該液態水的混合液開始反應產生氫氣。較佳地，該鐵金屬粉末與液態水混合之前，可經過一表面處理步驟，以去除鐵金屬粉末的表面雜質及其金屬氧化物。該表面處理步驟可使用稀釋酸液浸泡，其體積莫耳濃度較佳為0.1M，稀釋酸液的種類可例如為稀釋鹽酸、稀釋硝酸、稀釋硫酸、稀釋醋酸或其它種類酸液。In the method of hydrothermally producing hydrogen gas in the first embodiment of the present invention, first, an iron metal powder is provided. In this step, the iron metal powder may be a nano or micron-sized powder having a size of, for example, a particle diameter of from 100 nm to 10 μm. Subsequently, the iron metal powder and a liquid water are placed in a closed vessel and mixed to form a mixture of iron metal powder and liquid water. The manner of mixing is not limited, and the mixture may be made relatively uniform by stirring or may be left to stand still. Preferably, in the mixture of the iron metal powder and the liquid water, the iron metal powder is completely immersed in the liquid water, and the weight percentage of the iron metal powder may be between 5% and 60%, for example, 10%, 20 %, 30% or 40%. Next, the mixture is heated by a heating device to 100 ° C or higher, preferably 100 ° C to 200 ° C, and may be, for example, 120 ° C, 150 ° C or 180 ° C. At this time, the mixture of the iron metal powder and the liquid water starts to react to generate hydrogen gas. Preferably, the iron metal powder may be subjected to a surface treatment step to remove surface impurities of the iron metal powder and metal oxides thereof before being mixed with the liquid water. The surface treatment step may be immersed in a dilute acid solution, and the volume molar concentration thereof is preferably 0.1 M. The type of the diluted acid solution may be, for example, diluted hydrochloric acid, diluted nitric acid, diluted sulfuric acid, diluted acetic acid or other kinds of acid solution.
以本發明第一實施例之水熱法產生氫氣的方法所產生的氫氣，除了混合有小部分因加熱而蒸發的水蒸氣外，並無其他氣體存在，因此易於分離，得到純度高且便於利用的氫氣。其淨反應式如下：3 Fe+4 H2 O → Fe3 O4 +4 H2 The hydrogen produced by the method of generating hydrogen by the hydrothermal method according to the first embodiment of the present invention has no other gas except for a small amount of water vapor evaporated by heating, so that it is easy to separate, and the purity is high and the use is easy. Hydrogen. Its net reaction formula is as follows: 3 Fe+4 H 2 O → Fe 3 O 4 +4 H 2
此外，使用奈米或微米級的鐵金屬粉末可以增加液態水與鐵金屬表面的接觸總面積，使得反應速率隨之提高，產生氫氣的速度更加快速。In addition, the use of nano or micron-sized iron metal powder can increase the total contact area of liquid water with the surface of the iron metal, so that the reaction rate is increased and the rate of hydrogen generation is faster.
請參照第1圖所示，第1圖為本發明的一實施例之以水熱法產生氫氣的反應裝置側視圖。本發明設計製作完成一水熱法產生氫氣的反應裝置10，可用於加熱，以及收集產生的氫氣。該反應裝置包含：一反應 容器1，用以容置一鐵金屬粉末及一液態水的一混合液；一加熱裝置2，用以加熱該反應容器內之混合液，以反應產生氫氣；一冷卻裝置3，具有一第一開口部3a與一第二開口部3b，該第一開口部3a與該反應容器1之一開口1a緊密接合；以及一氣體收集筒4，與該冷卻裝置3之第二開口部3b緊密接合。該反應容器1由於需要承受加熱時所蒸發的水蒸氣以及氫氣產生時的壓力，因此較佳的是由耐壓材質製成，可例如為不鏽鋼。該反應容器1可選擇性地與一壓力偵測裝置(未繪示)連接，以隨時得知反應進行時所產生的氣體壓力。Referring to Fig. 1, Fig. 1 is a side view of a reaction apparatus for generating hydrogen gas by a hydrothermal method according to an embodiment of the present invention. The present invention contemplates a reaction apparatus 10 that produces a hydrothermal process to produce hydrogen, which can be used for heating and collecting the generated hydrogen. The reaction device comprises: a reaction a container 1 for accommodating a mixed liquid of iron metal powder and a liquid water; a heating device 2 for heating the mixed liquid in the reaction vessel to react to generate hydrogen; and a cooling device 3 having a first The opening portion 3a and a second opening portion 3b which are in close contact with the opening 1a of the reaction container 1 and a gas collecting cylinder 4 which is in close contact with the second opening portion 3b of the cooling device 3. The reaction vessel 1 is preferably made of a pressure-resistant material because it needs to withstand the water vapor evaporated during heating and the pressure at which hydrogen gas is generated, and may be, for example, stainless steel. The reaction vessel 1 can be selectively coupled to a pressure detecting device (not shown) to know the pressure of the gas generated during the reaction.
再者，該加熱裝置2係用以均勻加熱該反應容器1，可選擇性地與一溫控偵測裝置(未繪示)連接，以精確控制所需要的反應溫度於100℃至200℃。該冷卻裝置3係可選擇與地平面具有等於或小於90度的夾角，因此可利用重力作用使得該氫氣與水蒸氣冷凝後的液態水自動分離，該夾角可例如為30度、45度、60度或90度。接著，被分離的氫氣通過該第二開口部3b進入該氣體收集桶4，而冷凝後的液態水則通過該第一開口部3a回到該反應容器1中，繼續與鐵金屬粉末進行反應。該氣體收集筒4亦可選擇性地與一壓力偵測裝置(未繪示)連接，以隨時得知所產生的氫氣收集的狀況。Furthermore, the heating device 2 is for uniformly heating the reaction vessel 1, and is selectively connected to a temperature-controlled detecting device (not shown) to precisely control the required reaction temperature at 100 ° C to 200 ° C. The cooling device 3 can select an angle equal to or less than 90 degrees with the ground plane, so that the hydrogen can be automatically separated from the liquid water after the water vapor is condensed by gravity, and the angle can be, for example, 30 degrees, 45 degrees, 60 degrees. Degree or 90 degrees. Then, the separated hydrogen gas enters the gas collection tank 4 through the second opening portion 3b, and the condensed liquid water returns to the reaction vessel 1 through the first opening portion 3a to continue the reaction with the iron metal powder. The gas collecting cylinder 4 can also be selectively connected to a pressure detecting device (not shown) to know the condition of the generated hydrogen gas at any time.
此外，該第一開口部3a與該反應容器1之該開口1a之間可另設有一第一閥門5a，該第一閥門5a係用以控制反應後的混合氣體(包含水蒸氣及氫氣)是否通過冷卻裝置3，使得水蒸氣冷凝回到該反應容器1與氫氣分離。該第二開口部3b與該氣體收集筒4之間可另設有一第二閥門5b，以控制氫氣是否流通到該氣體收集筒4內。In addition, a first valve 5a for controlling the mixed gas (including water vapor and hydrogen) after the reaction may be additionally disposed between the first opening portion 3a and the opening 1a of the reaction vessel 1. The water vapor is condensed back to the reaction vessel 1 by the cooling device 3 to be separated from the hydrogen gas. A second valve 5b may be additionally disposed between the second opening portion 3b and the gas collecting cylinder 4 to control whether hydrogen gas flows into the gas collecting cylinder 4.
針對產生氫氣的效率，本發明之實驗數據以及圖表請參考下列說明。For the efficiency of generating hydrogen, the experimental data and graphs of the present invention are referred to the following description.
請參考第2圖所示，其係探討改變反應所使用的鐵金屬粉末含量重量百分比所造成的生產氫氣的影響。藉由改變微米級鐵金屬粉末(3微米)與混合液的重量百分比0%、10%、20%以及30%，觀察生產氫氣的量變化的結果。如第2圖所示，氫氣產量隨著鐵金屬粉末含量的增加而增加，並且在九小時內呈現穩定上升的趨勢。Please refer to Figure 2, which discusses the effect of hydrogen production on the weight percent of iron metal powder used to change the reaction. The result of the change in the amount of hydrogen produced was observed by changing the weight percentages of the micron-sized iron metal powder (3 μm) and the mixed liquid by 0%, 10%, 20%, and 30%. As shown in Fig. 2, the hydrogen production increased with the increase in the content of iron metal powder, and showed a steady upward trend within nine hours.
請再參考第3圖，其係探討改變反應時的溫度所造成的生產氫氣的影響。藉由改變不同反應溫度為30℃、90℃、120℃、135℃以及150℃，觀察生產氫氣的量變化的結果。此實驗中所使用的微米級鐵金屬粉末粒徑為3微米，及含量重量百分比為20%。如第3圖所示，氫氣產量在溫度低於100℃時產氫效果並不顯著，但在溫度150℃時，反應九小時可產生88 bar的氫氣(如第2圖所示)。如果改用奈米級鐵粉(100奈米，重量百分比為20%)，產氫速率可更明顯提升，隨溫度提高而提高，且在兩小時左右即達到平衡，如第4圖所示。因此可知，使用微米級或奈米級的鐵金屬粉末，在控制的時間內欲獲得較大的氫氣產量，溫度應大於100℃，較佳的是介於120℃至150℃之間。Please refer to Figure 3 again, which discusses the effect of hydrogen production caused by changing the temperature of the reaction. The results of the change in the amount of hydrogen produced were observed by changing the different reaction temperatures to 30 ° C, 90 ° C, 120 ° C, 135 ° C, and 150 ° C. The micron-sized iron metal powder used in this experiment had a particle size of 3 μm and a content by weight of 20%. As shown in Figure 3, hydrogen production is not significant at temperatures below 100 °C, but at 150 °C, 88 bar of hydrogen is produced for nine hours (as shown in Figure 2). If you switch to nano-sized iron powder (100 nm, 20% by weight), the rate of hydrogen production can be significantly increased, increased with increasing temperature, and reached equilibrium in about two hours, as shown in Figure 4. Therefore, it is known that the use of micron- or nano-sized iron metal powders requires a large hydrogen production rate within a controlled period of time, and the temperature should be greater than 100 ° C, preferably between 120 ° C and 150 ° C.
此外，由第3圖以及第4圖比較，可觀察到微米級與奈米級的鐵金屬粉末在90℃與120℃時的氫氣產量相差最大。以反應速率來看，奈米級鐵金屬粉末之產氫速率遠高於微米級鐵金屬粉末，這是因為鐵金屬粉末奈米化後可明顯提高反應的接觸表面積與活性。根據實驗結果，微米級的鐵金屬粉末在反應9小時及24小時之後，其轉化率分別為24.16%及45.09%；奈米級的鐵金屬粉末在90℃、120℃以及150℃下反應的轉化率分別為59.13%、63.38%及64.42%。Further, from the comparison of Fig. 3 and Fig. 4, it can be observed that the micron- and nano-scale iron metal powders have the largest difference in hydrogen production at 90 ° C and 120 ° C. In terms of reaction rate, the hydrogen production rate of the nano-sized iron metal powder is much higher than that of the micro-scale iron metal powder, because the contact surface area and activity of the reaction can be significantly improved after the iron metal powder is nano-ized. According to the experimental results, the conversion of micron-sized iron metal powder after reaction for 9 hours and 24 hours was 24.16% and 45.09%, respectively; the conversion of nano-sized iron metal powder at 90 ° C, 120 ° C and 150 ° C The rates were 59.13%, 63.38% and 64.42%, respectively.
綜上所述，本發明之以水熱法產生氫氣的方法及反應裝置，具有製程簡單易於大量生產的優勢，製得的氫氣由於純度高收集後即可利用。再者，本發明所使用的反應物為鐵金屬粉末以及液態水，兩者皆為容易取得且易於準備的材料，反應後的產物除了氫氣外僅有鐵金屬氧化物，不會造成環境汙染，其中鐵金屬粉末表面之金屬氧化物僅需簡單使用稀釋酸液清洗後即可回收再次利用，得以節省成本並符合目前的環保趨勢。In summary, the method and the reaction device for generating hydrogen by hydrothermal method have the advantages of simple process and mass production, and the obtained hydrogen can be utilized after being collected with high purity. Furthermore, the reactants used in the present invention are iron metal powder and liquid water, both of which are readily available and easy to prepare. The product after the reaction has only iron metal oxides other than hydrogen, and does not cause environmental pollution. The metal oxide on the surface of the iron metal powder can be recycled and reused simply by using the diluted acid solution, thereby saving cost and complying with the current environmental protection trend.
雖然本發明已以較佳實施例揭露，然其並非用以限制本發明，任何熟習此項技藝之人士，在不脫離本發明之精神和範圍內，當可作各種更動與修飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。The present invention has been disclosed in its preferred embodiments, and is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.
10‧‧‧反應裝置10‧‧‧Reaction device
1‧‧‧反應容器1‧‧‧Reaction vessel
1a‧‧‧開口1a‧‧‧ openings
2‧‧‧加熱裝置2‧‧‧heating device
3‧‧‧冷卻裝置3‧‧‧Cooling device
3a‧‧‧第一開口部3a‧‧‧First opening
3b‧‧‧第二開口部3b‧‧‧second opening
4‧‧‧氣體收集筒4‧‧‧ gas collection cylinder
5a‧‧‧第一閥門5a‧‧‧First valve
5b‧‧‧第二閥門5b‧‧‧second valve
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