.201210934 六、發明說明： 【發明所屬之技術領域】 本發明係關於用來從水製造出氫氣的氫氣之製造方法 【先前技術】 使用氫氣作爲燃料氣是以往所知悉的。作爲氫氣之製 造方法，已有許多發明被提出。例如，將水100重量份予 以熱分解而獲得氫氣的方法，或將硫酸熱分解而使用碘水 來取出氫氣的is法（Iodine-Sulfe)法等是已知的。IS法， 是經由本生反應步驟、碘化氫濃縮分解步驟、硫酸濃縮分 解步驟等的三步驟，而從水中將氫氣和氧氣分解並取出（ 專利文獻1 )。 除此外，作爲產生氫氣的方法，讓金屬合金和離子傳 導度低的水反應而產生氫氣的方法是已知的（專利文獻2 )。該專利文獻之氫氣，是在氫氣產生反應的開始段階， 將25°C的離子傳導度未達10ps/cm的水供應給氫氣產生物 質而獲得的。在此，氫氣產生物質，是使用鋁、矽、鋅、 鎂及以該等當中一種以上的金屬元素爲主體之合金，合金 中該一種以上的金屬含量爲60重量份以上，且含有80重量 份以上之粒徑1 00μιη以下的粒子。 在該專利文獻2，是使用具有特定形態和特定成分組 成的氫氣產生物質，在氫氣產生反應的開始段階，使用具 有特定離子傳導度的水，因此不須特別操作或特別的裝置 -5- 201210934 即可製造氫氣。例如在鋁、矽、鋅、鎂當中，鋁與水的反 應是經由（7 )〜（9 )之任一者來進行。 2Α1 + 6Η2〇-^Α12〇3·3Η2〇 + 3Η2...... ( η ) 2Α1 + 4Η20 —Α12〇3 ·Η20 + 3Η2...... ( 8 ) 2Α1 + 3Η20 —Α12〇3+3Η2...... (9) 氫氣產生物質是以粒子的形式來使用，粒子是由粒子 內部、以及被覆其之表面被覆膜所構成。即使在氫氣產生 物質形成有氧化物所構成之表面被覆膜，只要在氫氣產生 反應的開始段階將25°C的離子傳導度未達l〇pS/cm的水供 應給氫氣產生物質’即可縮短讓氫氣產生反應發生的時間 ’將到達最大氫氣產生量的時間縮短，而將氫氣產生效率 提高。 〔專利文獻1〕日本特開2005-41764 〔專利文獻2〕日本特開2007-326731 【發明內容】 將水100重量份予以熱分解而獲得氫氣的方法，由於 氫和氧的鍵結很強，理論上必須對水賦予3 000°C~5000°C的 溫度，才能分解成氫氣和氧氣。以3 00 0 °C以上的溫度將水 予以熱分解而獲得氫氣的方法，存在許多的問題，例如找 不到能獲得3000°C以上的高溫之實際方法、無法便宜地製 作出能保持這種高溫狀態的空間（不受外界影響）之設備 、找不到能對高溫空間內連續供應水的手段等，因此利用 水的熱分解來生成氫氣的想法，並無法實現。 201210934 專利文獻1所示的IS法，必須加熱至9 ο 0 °c左右的高溫 ，作爲其熱源必須使用高溫氣冷反應爐。該高溫氣冷反應 爐的製造成本高，而且是經由三個步驟來製造氫氣，爲了 製造氫氣的成本變得非常局，其成本效益比差，而未被採 用。 專利文獻2所示的氫氣之製造方法，氫氣產生物質是 使用鋁、矽、鋅、鎂及以該等當中一種以上的金屬元素爲 主體之合金’合金中該一種以上的金屬含量爲60重量份以 上，且含有80重量份以上粒徑ΙΟΟμιη以下的粒子。該氫氣 產生物質，相當耗費製造成本。此外，25。(：的離子傳導度 未達1 Ops/cm的水之製造也非常耗費製造成本。使用高成 本的氫氣產生物質和高成本的水來製造氫氣的情況，會有 氫氣製造時的材料費用變高的缺點。 再者，氫氣產生物質由於是粒子，混入水中後要和水 分離很困難。因此，讓氫氣產生物質與水反應而產生氫氣 後’想要停止讓氫氣產生的情況，要讓氫氣產生物質和水 分離很難’因此會有不容易立刻停止讓氫氣產生的缺點。 本發明是爲了提供一種便宜的氫氣之製造方法，可將 一般的水和市售化學品和市售金屬加入容器中，藉由反應 熱來製造氫氣。本發明的其他目的，是能立刻停止讓氫氣 產生。 爲了上述目的之本發明的氫氣之製造方法，其特徵在 於，是將100重量份的水、1重量份以上的鎂、以及5重量 份以上的檸檬酸在容器內混合，藉此在容器內產生氫氣。 201210934 本發明特徵在於，前述鎂的重量爲ι〇重量份以上。本發明 的特徵在於，前述檸檬酸的重量爲10重量份以上。本發明 的特徵在於，在前述容器內具備可上下移動自如的收容手 段，在前述收容手段內收容前述鎂，要產生氫氣的情況是 將前述鎂浸漬於前述容器內之檸檬酸水溶液的液面下，要 停止讓氫氣產生的情況，是讓前述收容手段上昇而將前述 鎂抬高到比容器內的檸檬酸水溶液之液面更上方。本發明 的特徵在於，在前述容器的下部附近設置用來從前述容器 內將水排往外部之排出管，在前述排出管的中途設置開閉 閥，要停止讓氫氣產生的情況，是從前述排出管將前述容 器內的水排出。本發明的特徵在於，加入前述容器內的水 ，是讓水最初通過離子交換樹脂，然後先通過電氣石、以 及含有二氧化矽65〜76重量份的岩石之任一方再通過另一 方，而藉此生成的特殊水；前述岩石是由流紋岩或花崗岩 當中至少一個所構成。本發明的特徵在於，在用來生成前 述特殊水之電氣石中混合有鋁、不鏽鋼、銀當中至少一種 的金屬。本發明的特徵在於，前述流紋岩爲黑曜石、真珠 岩、松脂岩當中至少一種所構成的岩石。 本發明的氫氣之製造方法所使用的是自來水等的一般 水、市售的鎂、以及市售的檸檬酸，將其等放入容器中而 利用反應熱產生氫氣。在專利文獻2的氫氣產生物質，是 含有80重量份以上之粒徑100μιη以下的粒子，在本發明， 除了一般水以外，僅使用市售的鎂及市售的檸檬酸（未使 用任何特殊材料），相較於習知的氫氣製造方法所使用的 -8- 201210934 材料，費用非常便宜。因此’能以低成本製造氫氣。此外 ，本發明所生成的殘留物爲檸檬酸鎂。該檸檬酸鎂可作爲 醫療用材料來使用，因此可降低總成本。 檸檬酸，由於可防止在鎂上形成膜，作爲鎂除了粉末 以外還能使用塊體。由於能使用鎂的塊體，可在收容手段 的棚架載置鎂的塊體，而讓收容手段在容器內昇降。要產 生氫氣的情況，將鎂浸漬於容器內的液面下。另一方面， 要停止讓氫氣產生的情況，只要將鎂抬高到比容器內的液 面更上方，即可讓鎂和檸檬酸水溶液分離，而立刻停止讓 氫氣產生。如此般，能立刻產生氫氣且能立刻停止讓氫氣 產生，而能將氫氣自由地使用於以氫氣爲能源之各種目的 〇 本發明所使用的水，不管是什麼種類的水都能產生氫 氣。但如果使用特殊水（創生水）的話，相較於使用其他 種類的水的情況由於氫氣產生時間更長，而能獲得更多的 氫氣量。該特殊水，是讓水最初通過離子交換樹脂，然後 先通過電氣石、以及含有二氧化矽65〜76重量份的岩石之 任一方再通過另一方，而藉此生成的；該岩石是由流紋岩 鹗花崗岩當中至少一個所構成。 【實施方式】 在說明本發明的氫氣之製造方法之前’首先根據第1 圖至第3圖來說明本發明所使用之特殊水（以下稱「創生 水j )。第1圖係顯示創生水的製造裝置之一實施例的構 -9 - 201210934 造圖。將第1軟水產生器10和第2軟水產生器12和離子產生 器14和岩石收納器16，透過連絡管18a、18b、18c依序串 列連結。在第1軟水產生器1 〇，例如自來水等的有壓力的 水是從水供應管20透過連絡管22供應至第1軟水產生器10 。在水供應管20和連絡管22之間，具備像水龍頭那樣的入 口用開閉閥24，在連絡管22的中途設置止回閥26。在岩石 收納器16的出口側安裝取出管28，在取出管28的前端或中 途具備出口用開閉閥30。 在自來水的情況，從水供應管20送出的水，依序經由 第1軟水產生器1〇、第2軟水產生器12、離子產生器14、岩 石收納器1 6，藉由打開出口用開閉閥3 0而從取出管2 8取出 。在自來水以外的情況，雖未圖示出，是藉由泵，將貯留 於水槽內的水經由水供應管20導入第1軟水產生器10。在 此情況，在泵和第1軟水產生器之間具備止回閥26。 如第2圖之截面圖所示，在第1軟水產生器10和第2軟 水產生器12的內部收納大量的粒狀之離子交換樹脂32。軟 水產生器10、12的主體34呈筒狀，在該筒狀的上下端面具 有水的出入口 3 6a、36b。在筒狀主體34的內部，在離上下 端面一段距離的內壁上，設置分別在中央穿設開孔之遮擋 構件38a、38b。在該一對的遮擋構件38a、38b之間配置： 收納有離子交換樹脂32之網40。在離上下的出入口 36a、 3 6b—段距離的內壁上設置在中央穿設開孔之遮擋構件38 ，是爲了將收納有離子交換樹脂32之網40配置在一對的遮 擋構件38之間，並在出口 36a、36b的附近形成空間42a、 •10- 201210934 42b。此外，讓水從遮擋構件38a、38b中央的開孔出入的 原因在於，必須讓水接觸離子交換樹脂32。將離子交換樹 脂32收納於網40的原因在於，爲了洗淨粒狀離子交換樹脂 3 2而將其取出時，能包括網40將粒狀離子交換樹脂32—起 取出。 第1軟水產生器10和第2軟水產生器I2，其高度例如爲 80cm ’內徑爲l〇cm。例如離子交換樹脂32的收納高度爲 7〇cm (在上下存在空間42a、42b )。這時，離子交換樹脂 3 2的收納高度，必須設定成能讓水充分進行離子交換的高 度。另一方面，若離子交換樹脂32的收納高度過高（例如 離子交換樹脂32的收納高度成爲約200cm以上），離子交 換樹脂32造成水的阻力而使通過軟水產生器內部的流量減 少，因此離子交換樹脂3 2的收納高度必須設定成不致減少 流量的高度。將收納離子交換樹脂32的容器分成2個的原 因在於：爲了將第1軟水產生器10和第2軟水產生器12的高 度降低成與離子產生器14、岩石收納器16相同程度的高度 ，又爲了避免通過其中的水因壓力損失而造成流量減少。 此外，將2個軟水產生器10、12合一而成爲1個軟水產生器 亦可。 離子交換樹脂32，是用來將水中所含的Ca2+、Mg2+、 Fe2 +等的金屬離子除去而使水成爲軟水，特別是用來使水 的硬度降低至接近零的程度。作爲離子交換樹脂32例如可 使用：將苯乙烯·二乙烯苯的球狀共聚物均一地磺化而成 之強酸性陽離子交換樹脂（RzS03Na)。該離子交換樹脂 S- -11 - 201210934 32和水中所含的Ca2+、Mg2+、Fe2 +等的金屬離子會產生以 下的離子交換反應。 2RzS03Na+Ca2 + ->(RzS03)2Ca + 2Na + 2RzS〇3Na + Mg2 + ->(RzS〇3)2Mg + 2Na + 2RzS03Na + Fe2 + 4(RzS03)2Fe + 2Na + 亦即，藉由通過離子交換樹脂32，可除去水中所含的 Ca2+、Mg2+、Fe2 +等。作爲離子交換樹脂32，藉由使用強 酸性陽離子交換樹脂（RzS03Na)，可產生鈉離子（Na + )。離子交換樹脂32雖然也能採用可產生Na+以外的，但 宜產生Na+。在水爲自來水的情況，自來水中除了 Ca2+、 Mg2+、Fe2 +等的金屬離子外雖還含有氯，但自來水通過離 子交換樹脂32後，該氯完全不會發生變化。 另一方面，水（H20)通過離子交換樹脂32會產生以 下的變化。 Η20->Η + + 0Η …(1 ) H20 + H + -^H30 + ··· ( 2 ) 亦即，如式（1 ) ( 2 )所示，藉由通過離子交換樹脂 32，能從水產生氫氧離子（ΟίΓ)和經離子（H30+)。 如此般，在水爲硬水的情況，藉由通過離子交換樹脂 32，會從水中除去Ca2+、Mg2+、Fe2 +等的金屬離子而成爲 軟水。此外，藉由通過離子交換樹脂32，會在水中產生 Na+、OH_、經離子（H30+)。但是，自水來中所含的氯（ C1)不會進行離子化而保持原狀態通過。此外，依離子交 換樹脂3 2的種類，也有不產生Na+的情況。 -12- 201210934 接著，第3圖係顯示前述離子產生器14之部分截面圖 。離子產生器1 4，是將複數個匣體44上下連續地串列連結 而構成。在各匣體44的內部收納：單純之粒狀的電氣石46 、或是粒狀的電氣石46和板狀的金屬48的混合物之任一方 。電氣石具有正電極和負電極，利用該正電極和負電極來 使水帶有波長4〜14/zm的電磁波，且將水的團簇切斷而產 生經離子（H30+)。帶有波長4〜14/zm的電磁波之能量爲 0.004watt/cm2。在此的電氣石46，可以是將電氣石粉碎而 構成的，也可以是市售之稱爲電氣石顆粒之電氣石混合體 (電氣石和陶瓷和氧化鋁（含有銀亦可）的重量比爲約10 :80:10)。該電氣石顆粒所含的陶瓷，是具有將正電極 和負電極分離的作用。在此，相對於陶瓷以重量比1 〇%以 上的比例混合電氣石46後在8 00 °C以上加熱，可製作出經 由水的攪拌而在既定期間（例如，直徑4mm時約3個月） 會磨耗掉的電氣石46。電氣石46經由加熱會增加強度，而 使磨耗期間變長。通過離子交換樹脂3 2後水會變成硬度接 近零的軟水，在該軟水中讓電氣石彼此摩擦。硬度接近 零的軟水，可防止鎂、鈣附著於電氣石46的負電極，而防 止電氣石46之正電極和負電面的作用降低。 作爲前述金屬48，是使用鋁、不鏽鋼、銀之至少1種 金屬。作爲該金屬48，宜使用在水中不生鏽、不溶於水的 金屬。在該金屬48當中，鋁具有殺菌、抗菌作用和漂白作 用，不鏽鋼具有殺菌、抗菌作用和洗淨提昇作用，銀具有 具有殺菌、抗菌作用。作爲金屬48，由於銅、給有毒性而 -13- 201210934 無法採用。此外，金等的高價材料基於成本考量而無法採 用。前述電氣石46和金屬48的重量比宜爲1〇: : 1〇。 若超過此範圍，一方的材料變得過多，而無法讓兩種材料 的效果同時發揮。 匣體44，是呈一端開口的筒狀，在其底面50設置多數 個孔52。在匣體44的內部放入電氣石46和金屬48的情況， 底面50的孔52的大小是設定成讓電氣石46、金屬48無法通 過。如第3圖所示，各匣體44，是以設有多數個孔52之底 面50朝下的方式，在該底面5〇上載置電氣石46、金屬48。 而且是設定成從下位朝上位流過各匣體44的內部。亦即， 在各匣體44，通過底面5 0的多數個孔52之水是從下往上朝 電氣石46和金屬48噴射。在此，由於自來水具有高水壓， 具有水壓的水會強烈衝擊匣體44內的電氣石46和金屬48， 因此是將孔52的大小及個數設定成：可利用該水的衝擊而 在匣體44內攪拌電氣石46和金屬48。將水朝電氣石噴射以 攪拌電氣石的理由在於：藉由該攪拌在電氣石和水產生摩 擦，以從電氣石讓正電極和負電極在水中溶出而將水的團 簇切斷，藉此大量地產生鋰離子（h3o+)。 作爲實際的設置例，是將收容容積爲內徑5 cm深7 cm 之匣體44重疊4段，在該匣體44內可充分收納電氣石46和 金屬48，但所收納之電氣石46和金屬48的分量是讓其等能 在匣體44內自由移動的分量。將匣體44的段數予以增減亦 可，採用收容容積較大的1個匣體44亦可。如此般’讓電 氣石46和金屬48分散在收容容積較小的複數個匣體44 ’並 -14 - 201210934 將該等複數個匣體44連結，可將利用水的衝擊之電氣石46 和金屬48的攪拌效率予以提昇。收納在匣體44內的電氣石 46，會溶在水中而在數個月後消滅，因此例如藉由螺合等 的手段而使各匣體44成爲容易拆裝，如此容易對各厘體44 內補充電氣石46。此外，金屬48因爲不溶於水而不須進行 補充，但將收納有電氣石46和金屬48之匣體44整體予以更 換也是可以的。匣體44是按照使用流量的大小而改變其收 容容積亦可。 爲了增加通過匣體44的水中所帶的負離子，可藉由讓 電氣石46彼此摩擦而產生正電極和負電極，讓該電氣石46 接觸水而達成負離子的增加。此外，爲了切斷水的團簇而 大量地產生經離子（H30+)，只要在匣體44內單純收容電 氣石46即可。但藉由讓金屬48和電氣石46混合，其等會互 相接觸而進一步增加電氣石4 6所產生的負離子。 由於電氣石46具有正電極和負電極，若用水攪拌電氣 石，水（H20 )會解離成氫離子（H+ )和氫氧離子（OH· )° h2o-»h++oh ··· ( 1 ) 再者，藉由氫離子（H+ )和水（H20 )，會產生具有 界面活性作用的鋰離子（H3o+)。該經離子（H30+ )的產 生量，是比藉由前述離子交換樹脂32所產生的量大得多。 Η20 + Η + οΗ30+·" ( 2 ) 該經離子（Η3ο+)的一部分會和水（Η20)結合，而 產生羥離子（Η3〇2·)和氫離子（Η+)。 -15- 201210934 Η 3 Ο + Η 2 Ο ~^ Η3Ο2 +2Η+." (3) 通過離子交換樹脂32後的水，藉由通過離子產生器14 ，會在其內部產生經離子（Η30+)、羥離子（η3ο2·)、 Η+、ΟΗ_。此外，通過離子交換樹脂32後的氯（Cl )和離 子交換樹脂32所產生的Na+，不會反應而能保持原狀地通 過離子產生器14。 通過離子產生器14後的水，接著通過岩石收納器16 ( 收納著：火成岩當中含有二氧化矽約65~76%的岩石54 )的 內部。火成岩（分成火山岩和深成岩）當中含有多量二氧 化矽的岩石54，在火山岩是包括黑曜石、真珠岩、松脂岩 等的流紋岩；在深成岩是包括花崗岩。在岩石收納器16的 內部，收納著黑曜石、真珠岩、松脂岩、花崗岩的岩石當 中至少1種以上的岩石。黑曜石、真珠岩、松脂岩等的流 紋岩、或是花崗岩是帶負電子。再者，黑曜石、真珠岩、 松脂岩等的流紋岩、花崗岩是屬於酸性岩。流紋岩具有與 花崗岩相同的化學組成。 該等火成岩當中含有約65〜76%二氧化矽的岩石（黑曜 石、真珠岩、松脂岩等的流紋岩、或是花崗岩等的深成岩 )，在原石的狀態具有-20〜-240mV的氧化還原電位。但岩 石54是將可溶於水中者除外。岩石收納器16例如爲內徑 10cm、高度80cm的筒狀物，在其內部以不致降低水的通 過流量的分量收容著：例如大小5〜5 0mm左右的火成岩當 中之含有多量二氧化矽的岩石54。 通過離子產生器14後的水，若通過該岩石收納器16的 -16- 201210934 內部，會對水附加e·(負電子）。結果，藉由負電子使自 來水中的氯（C1)變成氯離子。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing hydrogen gas for producing hydrogen gas from water. [Prior Art] It has been conventionally known to use hydrogen as a fuel gas. As a method of producing hydrogen, many inventions have been proposed. For example, a method in which 100 parts by weight of water is thermally decomposed to obtain hydrogen gas, or an isodine-sulfe method in which sulfuric acid is thermally decomposed and iodine water is used to extract hydrogen gas is known. In the IS method, hydrogen gas and oxygen gas are decomposed and taken out from water (three patents) through three steps of a bio-reaction step, a hydrogen iodide concentration and decomposition step, and a sulfuric acid concentration and decomposition step (Patent Document 1). In addition, as a method of generating hydrogen gas, a method of reacting a metal alloy with water having a low ion conductivity to generate hydrogen gas is known (Patent Document 2). The hydrogen of this patent document is obtained by supplying water having an ion conductivity of less than 10 ps/cm at 25 ° C to a hydrogen generating material at the beginning of the hydrogen generation reaction. Here, the hydrogen generating material is aluminum, cerium, zinc, magnesium, and an alloy mainly composed of one or more of these metal elements, and the one or more metal content in the alloy is 60 parts by weight or more and 80 parts by weight. The above particles having a particle diameter of 1 00 μm or less. In this Patent Document 2, a hydrogen generating substance having a specific form and a specific component composition is used, and water having a specific ion conductivity is used at the beginning of the hydrogen generating reaction, so that no special operation or special device is required -5 - 201210934 Hydrogen can be produced. For example, among aluminum, bismuth, zinc, and magnesium, the reaction of aluminum with water is carried out by any of (7) to (9). 2Α1 + 6Η2〇-^Α12〇3·3Η2〇+ 3Η2...... ( η ) 2Α1 + 4Η20 —Α12〇3 ·Η20 + 3Η2...... ( 8 ) 2Α1 + 3Η20 —Α12〇3 +3Η2 (9) The hydrogen generating substance is used in the form of particles, and the particles are composed of the inside of the particles and the surface coating film covering the particles. Even if a surface coating film composed of an oxide formed of a hydrogen generating substance is formed, water having an ion conductivity of less than 10 〇 pS/cm at 25 ° C can be supplied to the hydrogen generating substance at the beginning of the hydrogen generating reaction. Shortening the time for the hydrogen generation reaction to occur 'the time to reach the maximum hydrogen generation amount is shortened, and the hydrogen generation efficiency is improved. [Patent Document 1] JP-A-2005-41764 [Patent Document 2] JP-A-2007-326731 [Disclosed] A method of thermally decomposing 100 parts by weight of water to obtain hydrogen gas, since hydrogen and oxygen are strongly bonded, In theory, water must be given a temperature of 3 000 ° C ~ 5000 ° C in order to decompose into hydrogen and oxygen. There are many problems in the method of thermally decomposing water at a temperature of 300 ° C or higher to obtain hydrogen gas. For example, there is no practical method for obtaining a high temperature of 3000 ° C or higher, and it is not possible to inexpensively produce such a method. The equipment in the high-temperature space (not affected by the outside world) cannot find a means for continuously supplying water to the high-temperature space. Therefore, the idea of generating hydrogen by thermal decomposition of water cannot be realized. 201210934 The IS method disclosed in Patent Document 1 must be heated to a high temperature of about 9 ο ° ° C. As a heat source, a high-temperature gas-cooled reactor must be used. The high-temperature gas-cooled reactor is expensive to manufacture, and hydrogen is produced in three steps. The cost for producing hydrogen becomes very low, and the cost-benefit ratio is poor, and it is not used. In the method for producing hydrogen gas according to Patent Document 2, the hydrogen generating material is an alloy of aluminum, lanthanum, zinc, magnesium, and a metal element mainly composed of one or more of the above, and the metal content of the one or more metals is 60 parts by weight. In the above, 80 parts by weight or more of particles having a particle diameter of ΙΟΟμηη or less are contained. This hydrogen generating material is quite expensive to manufacture. In addition, 25. (The production of water with an ion conductivity of less than 1 Ops/cm is also very costly to manufacture. The use of high-cost hydrogen generating materials and high-cost water to produce hydrogen may result in higher material costs for hydrogen production. Disadvantages. Further, since the hydrogen generating substance is a particle, it is difficult to separate it from water after it is mixed into water. Therefore, after the hydrogen generating substance reacts with water to generate hydrogen, it is necessary to stop the hydrogen generation. It is difficult to separate matter and water. Therefore, there is a disadvantage that it is not easy to stop the hydrogen generation immediately. The present invention is to provide an inexpensive method for producing hydrogen, which can be used to add general water and commercially available chemicals and commercially available metals to a container. Hydrogen is produced by heat of reaction. Another object of the present invention is to immediately stop the production of hydrogen. The method for producing hydrogen according to the present invention for the above purpose is characterized in that 100 parts by weight of water and 1 part by weight are used. The above magnesium and 5 parts by weight or more of citric acid are mixed in a container, thereby generating hydrogen gas in the container. 201210934 The present invention is characterized in that In the present invention, the weight of the citric acid is 10 parts by weight or more. The present invention is characterized in that the container has a storage means that can be moved up and down, and the storage means is provided. In the case where the magnesium is contained in the means, the hydrogen is generated by immersing the magnesium in the liquid surface of the aqueous citric acid solution in the container, and stopping the hydrogen generation, and raising the magnesium to raise the magnesium to the storage means. The present invention is characterized in that a discharge pipe for discharging water from the inside of the container to the outside is provided in the vicinity of a lower portion of the container, and an opening and closing valve is provided in the middle of the discharge pipe. To stop the generation of hydrogen, the water in the container is discharged from the discharge pipe. The present invention is characterized in that the water added to the container is such that the water initially passes through the ion exchange resin and then passes through the tourmaline, And any one of the rocks containing 65 to 76 parts by weight of cerium oxide and passing through the other side, thereby generating special water The rock is composed of at least one of rhyolite or granite. The present invention is characterized in that a metal of at least one of aluminum, stainless steel and silver is mixed in the tourmaline for generating the aforementioned special water. The rhyolite is a rock composed of at least one of obsidian, nacre, and rosin. The method for producing hydrogen according to the present invention uses general water such as tap water, commercially available magnesium, and commercially available citric acid. The hydrogen generating material of Patent Document 2 contains 80 parts by weight or more of particles having a particle diameter of 100 μm or less. In the present invention, only commercially available, except for general water, is used. Magnesium and commercially available citric acid (without using any special materials) are very inexpensive compared to the conventional -8-201210934 material used in the hydrogen production process. Therefore, hydrogen can be produced at low cost. Further, the residue produced by the present invention is magnesium citrate. The magnesium citrate can be used as a medical material, thereby reducing the total cost. Citric acid can prevent the formation of a film on magnesium, and a bulk can be used as a powder in addition to powder. Since the magnesium block can be used, the magnesium block can be placed on the scaffold of the storage means, and the storage means can be raised and lowered in the container. In the case of generating hydrogen, the magnesium is immersed under the liquid surface in the container. On the other hand, to stop the hydrogen generation, as long as the magnesium is raised above the liquid level in the vessel, the magnesium and citric acid aqueous solution can be separated, and the hydrogen gas is immediately stopped. In this way, hydrogen can be generated immediately and hydrogen can be stopped immediately, and hydrogen can be freely used for various purposes of using hydrogen as an energy source. 水 The water used in the present invention can generate hydrogen regardless of the type of water. However, if special water (creative water) is used, it is possible to obtain more hydrogen gas because the hydrogen generation time is longer than in the case of using other types of water. The special water is formed by allowing water to initially pass through the ion exchange resin, and then passing through the tourmaline and one of the rocks containing 65 to 76 parts by weight of cerium oxide and then passing through the other side; At least one of the shale and granite is composed. [Embodiment] Before describing the method for producing hydrogen gas according to the present invention, first, the special water used in the present invention (hereinafter referred to as "created water j") will be described based on Fig. 1 to Fig. 3. Fig. 1 shows creation A configuration of an embodiment of a water-making apparatus - 201210934. The first soft water generator 10 and the second soft water generator 12, the ion generator 14 and the rock receiver 16 are passed through the connecting tubes 18a, 18b, 18c. In the first soft water generator 1 〇, pressurized water such as tap water is supplied from the water supply pipe 20 through the connection pipe 22 to the first soft water generator 10. The water supply pipe 20 and the connection pipe are provided. An inlet opening and closing valve 24 such as a faucet is provided between the 22, and a check valve 26 is provided in the middle of the connection pipe 22. The take-out pipe 28 is attached to the outlet side of the rock storage device 16, and an outlet is provided at the front end or the middle of the take-up pipe 28. The on-off valve 30 is used. In the case of tap water, the water sent from the water supply pipe 20 passes through the first soft water generator 1 〇, the second soft water generator 12, the ion generator 14, and the rock hopper 1 6 in this order. Open the outlet opening and closing valve 30 and remove the tube 2 8 In addition to the tap water, the water stored in the water tank is introduced into the first soft water generator 10 via the water supply pipe 20 by a pump. In this case, the pump and the first soft water are generated. A check valve 26 is provided between the devices. As shown in the cross-sectional view of Fig. 2, a large amount of granular ion exchange resin 32 is accommodated in the first soft water generator 10 and the second soft water generator 12. The soft water generator 10 The main body 34 of the tube 12 has a tubular shape, and has water inlets and outlets 36a and 36b on the upper and lower end faces of the cylinder. The inner side of the cylindrical body 34 is disposed at the center on the inner wall at a distance from the upper and lower end faces. The shutter members 38a and 38b are opened. Between the pair of shutter members 38a and 38b, a net 40 in which the ion exchange resin 32 is housed is disposed on the inner wall of the upper and lower inlet and outlet ports 36a and 36b. The shutter member 38 having the opening in the center is for arranging the net 40 in which the ion exchange resin 32 is housed between the pair of shielding members 38, and forming a space 42a in the vicinity of the outlets 36a and 36b, • 10-201210934 42b. In addition, let water from the blocking member 38a The reason for the opening and exit of the center of 38b is that water must be brought into contact with the ion exchange resin 32. The reason why the ion exchange resin 32 is stored in the net 40 is that when the granular ion exchange resin 3 2 is washed and taken out, The granular water ion exchange resin 32 is taken up by the mesh 40. The first soft water generator 10 and the second soft water generator I2 have a height of, for example, 80 cm 'the inner diameter is 10 cm. For example, the storage height of the ion exchange resin 32 is 7 〇cm (spaces 42a and 42b are present in the upper and lower sides). At this time, the storage height of the ion exchange resin 32 must be set to a level at which the water can be sufficiently ion exchanged. On the other hand, if the storage height of the ion exchange resin 32 is too high (for example, the storage height of the ion exchange resin 32 is about 200 cm or more), the ion exchange resin 32 causes water resistance and reduces the flow rate inside the soft water generator, so the ions are The storage height of the exchange resin 3 2 must be set to a height that does not reduce the flow rate. The reason why the container accommodating the ion exchange resin 32 is divided into two is that the heights of the first soft water generator 10 and the second soft water generator 12 are reduced to the same level as the ion generator 14 and the rock container 16, and In order to avoid the flow of water passing through it due to pressure loss. Further, the two soft water generators 10 and 12 may be combined to form one soft water generator. The ion exchange resin 32 is used to remove metal ions such as Ca2+, Mg2+, and Fe2+ contained in water to make water soft water, and particularly to reduce the hardness of water to near zero. As the ion exchange resin 32, for example, a strongly acidic cation exchange resin (RzS03Na) obtained by uniformly sulfonating a spherical copolymer of styrene-divinylbenzene can be used. The ion exchange resin S--11 - 201210934 32 and the metal ions such as Ca2+, Mg2+, Fe2+ contained in the water generate the following ion exchange reaction. 2RzS03Na+Ca2+ ->(RzS03)2Ca + 2Na + 2RzS〇3Na + Mg2 + ->(RzS〇3)2Mg + 2Na + 2RzS03Na + Fe2 + 4(RzS03)2Fe + 2Na + that is, by The ion exchange resin 32 removes Ca2+, Mg2+, Fe2+, and the like contained in the water. As the ion exchange resin 32, sodium ions (Na + ) can be produced by using a strongly acidic cation exchange resin (RzS03Na). The ion exchange resin 32 can also be used other than Na+, but Na+ is preferably produced. In the case where the water is tap water, the tap water contains chlorine in addition to metal ions such as Ca2+, Mg2+, and Fe2+, but the tap water does not change completely after the tap water passes through the ion exchange resin 32. On the other hand, water (H20) undergoes the following changes through the ion exchange resin 32. Η20->Η + + 0Η (1) H20 + H + -^H30 + (2) That is, as shown by the formula (1) (2), by passing through the ion exchange resin 32, Water produces hydroxide ions (ΟίΓ) and ions (H30+). In the case where the water is hard water, the ion exchange resin 32 removes metal ions such as Ca2+, Mg2+, and Fe2+ from the water to become soft water. Further, by passing through the ion exchange resin 32, Na+, OH_, and ion (H30+) are generated in water. However, chlorine (C1) contained in the water does not ionize and remains in the original state. Further, depending on the type of the ion exchange resin 3 2, Na + may not be generated. -12- 201210934 Next, Fig. 3 shows a partial cross-sectional view of the aforementioned ion generator 14. The ion generator 14 is configured by continuously connecting a plurality of corpses 44 in series. Inside each of the bodies 44, either a simple granular tourmaline 46 or a mixture of a granular tourmaline 46 and a plate-shaped metal 48 is housed. The tourmaline has a positive electrode and a negative electrode, and the positive electrode and the negative electrode are used to cause water to carry electromagnetic waves having a wavelength of 4 to 14/zm, and the cluster of water is cut to generate ions (H30+). The energy of an electromagnetic wave having a wavelength of 4 to 14/zm is 0.004 watt/cm2. The tourmaline 46 here may be formed by pulverizing tourmaline, or may be a commercially available tourmaline mixture called tourmaline particles (the weight ratio of tourmaline and ceramics and alumina (including silver) may be About 10:80:10). The ceramic contained in the tourmaline particles has a function of separating the positive electrode and the negative electrode. Here, the tourmaline 46 is mixed with the ceramic at a weight ratio of 1% by weight or more, and then heated at 800 ° C or higher to produce a predetermined period of time (for example, about 3 months at a diameter of 4 mm) by stirring with water. The tourmaline 46 will be worn away. The tourmaline 46 increases the strength by heating, and the wear period becomes longer. After passing through the ion exchange resin 3 2, the water becomes soft water having a hardness close to zero, and the tourmaline rubs against each other in the soft water. The soft water having a hardness close to zero prevents magnesium and calcium from adhering to the negative electrode of the tourmaline 46, and prevents the action of the positive electrode and the negative electrode surface of the tourmaline 46 from being lowered. As the metal 48, at least one metal of aluminum, stainless steel, and silver is used. As the metal 48, a metal which does not rust or dissolve in water in water is preferably used. Among the metals 48, aluminum has bactericidal, antibacterial and bleaching effects, stainless steel has bactericidal, antibacterial and washing and lifting effects, and silver has bactericidal and antibacterial effects. As the metal 48, due to the toxicity of copper, it is not possible to use -13-201210934. In addition, high-priced materials such as gold cannot be used based on cost considerations. The weight ratio of the tourmaline 46 to the metal 48 is preferably 1 〇: : 1 〇. If it exceeds this range, one of the materials becomes too much, and the effect of the two materials cannot be exerted at the same time. The body 44 has a cylindrical shape with one end open, and a plurality of holes 52 are provided in the bottom surface 50 thereof. When the tourmaline 46 and the metal 48 are placed inside the body 44, the size of the hole 52 of the bottom surface 50 is set such that the tourmaline 46 and the metal 48 cannot pass. As shown in Fig. 3, each of the bodies 44 is such that the bottom surface 50 of the plurality of holes 52 faces downward, and the tourmaline 46 and the metal 48 are placed on the bottom surface 5〇. Further, it is set to flow through the inside of each of the bodies 44 from the lower position to the upper position. That is, in each of the bodies 44, the water passing through the plurality of holes 52 of the bottom surface 50 is ejected from the bottom to the tourmaline 46 and the metal 48. Here, since the tap water has a high water pressure, the water having the water pressure strongly attacks the tourmaline 46 and the metal 48 in the body 44, so the size and the number of the holes 52 are set such that the impact of the water can be utilized. Tourmaline 46 and metal 48 are agitated within carcass 44. The reason why the water is sprayed toward the tourmaline to stir the tourmaline is that friction is generated in the tourmaline and water by the stirring, so that the positive electrode and the negative electrode are dissolved in the water from the tourmaline, and the cluster of water is cut off. Lithium ions (h3o+) are produced. As an actual installation example, the body 44 having a housing volume of 5 cm and an inner diameter of 5 cm is overlapped by four stages, and the tourmaline 44 and the metal 48 can be sufficiently accommodated in the body 44, but the stored tourmaline 46 and The component of the metal 48 is a component that allows it to move freely within the body 44. It is also possible to increase or decrease the number of segments of the body 44, and it is also possible to use one body 44 having a large housing volume. In this way, 'the tourmaline 46 and the metal 48 are dispersed in a plurality of carcasses 44 having a small storage volume 44' and -14 - 201210934, the plurality of carcasses 44 are connected, and the impact of the tourmaline 46 and the metal can be utilized. The stirring efficiency of 48 is improved. The tourmaline 46 accommodated in the body 44 is dissolved in water and is destroyed after several months. Therefore, each of the bodies 44 can be easily attached and detached by, for example, screwing, so that it is easy to apply to each of the bodies 44. Fill the tourmaline 46 inside. Further, the metal 48 is not required to be replenished because it is insoluble in water, but it is also possible to replace the entire body 44 in which the tourmaline 46 and the metal 48 are accommodated. The body 44 may be changed in accordance with the amount of flow used. In order to increase the negative ions carried in the water passing through the body 44, the positive electrode and the negative electrode can be generated by rubbing the tourmaline 46 with each other, and the tourmaline 46 is brought into contact with water to achieve an increase in negative ions. Further, in order to cut off the cluster of water and generate a large amount of ions (H30+), it is sufficient to simply house the electric gas 46 in the body 44. However, by mixing the metal 48 and the tourmaline 46, they will contact each other to further increase the negative ions generated by the tourmaline 46. Since the tourmaline 46 has a positive electrode and a negative electrode, if the tourmaline is stirred with water, the water (H20) will dissociate into hydrogen ions (H+) and hydroxide ions (OH·) ° h2o-»h++oh ··· ( 1 Further, lithium ions (H3o+) having an interfacial activity are generated by hydrogen ions (H+) and water (H20). The amount of the ion (H30+) produced is much larger than that produced by the aforementioned ion exchange resin 32. Η20 + Η + οΗ30+·" ( 2 ) A part of the ion (Η3ο+) combines with water (Η20) to produce hydroxyl ions (Η3〇2·) and hydrogen ions (Η+). -15- 201210934 Η 3 Ο + Η 2 Ο ~^ Η3Ο2 +2Η+." (3) Water passing through the ion exchange resin 32, by passing through the ion generator 14, generates ions (Η30+) inside it. Hydroxyl ion (η3ο2·), Η+, ΟΗ_. Further, the chlorine (Cl) after the ion exchange resin 32 and the Na+ generated by the ion exchange resin 32 can pass through the ion generator 14 without being reacted. The water that has passed through the ion generator 14 is then passed through the inside of the rock receiver 16 (containing: rock 54 containing about 65 to 76% of cerium oxide in the igneous rock). The igneous rock (divided into volcanic rocks and deep diagenes) contains a large amount of strontium dioxide 54. The volcanic rocks are rhyolites including obsidian, nacre, rosin, etc.; in deep rocks, including granite. In the rock container 16, at least one type of rock is contained in the rock of obsidian, nacre, rosin, and granite. Rhyolites such as obsidian, pearlite, rosin, or granite are negative electrons. Furthermore, rhyolites and granites such as obsidian, pearlite, and rosin are acidic rocks. Rhyolite has the same chemical composition as granite. These igneous rocks contain rocks of about 65 to 76% of cerium oxide (the rhyolite of obsidian, pearlite, rosin, or deep diagenes such as granite), and have a redox of -20 to 240 mV in the state of the original stone. Potential. However, rock 54 is excluded from being soluble in water. The rock container 16 is, for example, a cylindrical body having an inner diameter of 10 cm and a height of 80 cm, and is housed therein with a component that does not reduce the flow rate of water: for example, a rock containing a large amount of cerium oxide among igneous rocks having a size of about 5 to 50 mm. 54. When the water that has passed through the ion generator 14 passes through the inside of -16-201210934 of the rock container 16, e (negative electron) is added to the water. As a result, chlorine (C1) in the tap water is changed to chloride ion by a negative electron.
Cl + e'->Cl' ··· ( 4 ) 該cr和前述Na+以離子形式成爲穩定的狀態。穩定狀 態是指：不會蒸發而能長期保持離子狀態。此外，前述羥 離子（Η302·)也是以離子形式成爲穩定的狀態。藉由讓 水通過岩石54，比起通過離子產生器14的水，會產生更多 的經離子（Η30+)，且產生更多的羥離子（Η3 02_)、氫 離子（Η+)。 Η2〇 + Η + ^Η3〇+··· ( 2 ) H30 + + H2〇4H3 02- + 2H+.·. (3) 藉由讓水通過岩石54，除此外也會產生以下的反應。 0Η +Η + ^Η20··· ( 5 ) 2H + + 2e、2H2··. ( 6 ) 再者，若水通過岩石收納器16，藉由岩石54的負電子 ，水的氧化還原電位從+340mV變成-20~-240mV。若取代 水而使用熱水，負的氧化還原電位會變得更穩定。再者， 通過岩石54後的水含有大量的溶存氧和活性氫。 如第1圖所示，水最初是通過離子交換樹脂，接著通 過電氣石46 (或是電氣石46和金屬48的混合物），之後通 過岩石收納器1 6而成爲特殊水（創生水）。在創生水含有 多量的Na+、CP、H+、ΟΗ·、H2、經離子（H30+ )、羥離 子（Η3 02·)、活性氫、溶存氧。該水具有：能量爲0.004 watt/cm2之波長4~14ym的電磁波，且具有-20~-240mV的 -17- 201210934 氧化還原電位。 本發明之氫氣之製造方法所使用的水’是讓水依序通 過離子交換樹脂32、電氣石46 (或是電氣石46和金屬48的 混合物）、岩石5 4而獲得的創生水。如第1圖所示’水是 依序通過離子交換樹脂32、電氣石46 (或是電氣石46和金 屬48的混合物）、岩石54;但讓水依序通過離子交換樹脂 32、岩石54、電氣石46(或是電氣石46和金屬48的混合物 )亦可。亦即，如第4圖所示，讓水依序通過第1軟水產生 器10、第2軟水產生器12、岩石收納器16、離子產生器14 亦可。 在第4圖，通過離子交換樹脂32後的水，接著通過岩 石54。藉由該岩石54,在水內部產生e·(負電子）。結果 ，藉由負電子使自來水中的氯（C1)變成氯離子。Cl + e'->Cl' (4) The cr and the aforementioned Na+ are in a stable state in the form of ions. Stable state means that it does not evaporate and can maintain an ion state for a long time. Further, the aforementioned hydroxyl ions (Η302·) are also in a stable state in the form of ions. By passing water through the rock 54, more ions (Η30+) are produced than water passing through the ion generator 14, and more hydroxyl ions (Η3 02_) and hydrogen ions (Η+) are produced. Η2〇 + Η + ^Η3〇+··· (2) H30 + + H2〇4H3 02- + 2H+. (3) By allowing water to pass through the rock 54, the following reaction is also produced. 0Η +Η + ^Η20··· ( 5 ) 2H + + 2e, 2H2 · (6) Further, if water passes through the rock receiver 16, the redox potential of the water is from +340 mV by the negative electron of the rock 54. It becomes -20~-240mV. If hot water is used instead of water, the negative redox potential will become more stable. Furthermore, the water passing through the rock 54 contains a large amount of dissolved oxygen and active hydrogen. As shown in Fig. 1, the water is initially passed through an ion exchange resin, followed by tourmaline 46 (or a mixture of tourmaline 46 and metal 48), and then passed through rock reservoir 16 to become special water (creative water). The creation water contains a large amount of Na+, CP, H+, ΟΗ·, H2, ion (H30+), hydroxyl ion (Η3 02·), active hydrogen, and dissolved oxygen. The water has an electromagnetic wave having a wavelength of 4 to 14 μm at an energy of 0.004 watt/cm 2 and has an oxidation-reduction potential of -17 to 201210934 of -20 to 240 mV. The water used in the method for producing hydrogen according to the present invention is water generated by sequentially passing water through the ion exchange resin 32, tourmaline 46 (or a mixture of tourmaline 46 and metal 48), and rock 54. As shown in Fig. 1, the water passes through the ion exchange resin 32, the tourmaline 46 (or a mixture of the tourmaline 46 and the metal 48), and the rock 54; however, the water is sequentially passed through the ion exchange resin 32, the rock 54, Tourmaline 46 (or a mixture of tourmaline 46 and metal 48) may also be used. That is, as shown in Fig. 4, water may be sequentially passed through the first soft water generator 10, the second soft water generator 12, the rock receiver 16, and the ion generator 14. In Fig. 4, the water after passing through the ion exchange resin 32 is passed through the rock 54. With this rock 54, e·(negative electron) is generated inside the water. As a result, chlorine (C1) in the tap water is changed to chloride ions by negative electrons.
Cl + e'-^Cl'··· ( 4 ) 該cr和藉由離子交換樹脂3 2所產生之Na+，是以離子 形式成爲穩定的狀態。又通過離子交換樹脂3 2後的水也會 有不含Na +的情況。 通過離子交換樹脂32的水中，如前述式（1 )( 2 )所 示，存在著H+、OH_、經離子（H30+ )。通過離子交換樹 脂3 2後的水，然後藉由通過岩石54而產生以下的反應。 0Η· + Η + ->Η20 …（5 ) Η2〇 + Η + ^Η3〇 + · · ( 2 ) 2H + + 2e'-^2H2- ( 6) 在該反應中，比起藉由離子交換樹脂32所產生的量， -18- 201210934 會產生更多量的鍟離子（H3〇 ) ° 如以上所說明，藉由在離子交換樹脂32後再通過岩石 54，在水中會存在著：以往就有的Na+、〇『，新產生的 C1·、經離子（H3〇+ ) °此外’通過岩石54後的水的氧化 還原電位成爲_20~-240mV。若取代水而使用熱水，負的氧 化還原電位會變得更穩定。再者’通過岩石54後的水含有 大量的溶存氧和活性氫° 通過岩石54後的水’接著通過內藏有電氣石46和金屬 48之離子產生器14的內部。藉此產生以下的反應。 H2〇-^H + + OH'··· ( 1 ) Η20 + Η + — Η30+... ( 2 ) 該經離子（h3o+)會大量產生。又經離子（H30+)的 一部分會變成羥離子（Her)。 H30 + + H20-»H302 +2H+... (3) 結果，通過電氣石46和金屬48後的水中’經離子（ H30+)、羥離子（Η302·) 、〇H·、H +的量會增加。 如第4圖所示，依序通過離子交換樹脂32、岩石54、 電氣石46 (或是電氣石46和金屬48的混合物）後的水中， 含有 Na+、Cl·、ΟΗ·、經離子（Η30+)、羥離子（Η302·) 、Η+、活性氫、溶存氧，是包含與第1圖所產生的創生水 相同的成分。該水具有：能量爲〇.〇〇4watt/cm2之波長4〜14 // m的電磁波，且具有-20~-24〇mV的氧化還原電位。結果 ，第4圖所產生的水和第1圖所產生的創生水具有相同的效 果。依據第4圖的裝置所產生的水，其所含的成分與第1圖 -19 - 201210934 所產生的創生水結果是相同的，因此第4圖的裝置所產生 的水也是創生水。 以下顯示該創生水的水質檢査結果。與該創生水比較 之自來水的數値用括號代表。若自來水和創生水的數値相 同，則標示爲「相同」。亞硝酸性氮及硝酸性氮：1.8mg/l (相同），氯離子：6.8mg/l(9_Omg/l)，一般細菌：〇個 /ml (相同），氰離子：未達〇.〇1 mg/1 (相同），水銀： 未達0.0005 mg/1 (相同），有機磷：未達〇.1 mg/1 (相同 )，銅：未達0.01 mg/1 (相同），鐵：未達0.05 mg/1 (未 達0.08 mg/1)，錳：未達〇.〇1 mg/1 (相同），鋅：未達 0.005 mg/1 (未達 0.054 mg/1)，鉛：未達 0.01 mg/1 (相同 )，六價鉻：未達0.02 mg/1 (相同），鎘：未達0.005 mg/1 (相同），砷：未達0.005 mg/1 (相同），氟：未達 〇.15mg/l (相同），鈣、鎂等（硬度）：1.2mg/l(49.0 mg/1 )，酚類：未達0.005 mg/1 (相同），陰離子界面活 性劑：未達0.2 mg/1 (相同），pH値：6.9 (相同），臭氣 :無異臭（相同），味道：無異味（相同），色度：2度 (相同），濁度：〇度（1度）。 創生水具有以下所列舉的許多特徵。 (a) 含有經離子（H30+)、羥離子（h3〇2_)、氫離 子（H+)、氫、羥基（OH_)、硫酸離子（S〇4>)、碳酸 氫離子（HC03_)、碳酸離子（CO/—)、甲矽酸（H2Si03 )、游離二氧化碳（C02 )。 (b) 具有界面活性作用 -20- 201210934 具有界面活性作用（OW型創生水乳化作用）。 (C )具有微弱能量（育成光線）作用 電氣石會放出微弱能量（波長4〜14/zm的電磁波）。 該微弱能量會將水的大團簇切斷，而將團簇內之有毒氣體 、重金屬類排放到水的外部。 (d )具有-20〜-24 0mV的氧化還原電位。 (e) 含有溶存氧和活性氫。 (f) 是除去鈣離子、鎂離子後的軟水。 讓自來水等通過離子交換樹脂，可將水中所含的鈣離 子及鎂離子除去。 (g) 含有活性碳酸氫離子（HCOT )、甲矽酸（ H2Si03)。 接下來，根據第5圖來說明本發明的氫氣之製造方法 。本發明的氫氣之製造方法，是使用水、檸檬酸、鎂來製 造氫氣。本發明的氫氣之製造方法，是使用在內部收容水 、檸檬酸、鎂的容器60。容器60是由主體62和其蓋體64所 構成。容器60的材料，例如可使用玻璃和金屬等之家庭內 所使用之各種容器的材質。亦即，在本發明，由於容器60 內不是高壓，容器60不須使用特殊材料亦可。在容器60設 有：用來從外部朝向內部供應檸檬酸水溶液之水溶液導入 管66，可從外部朝向容器60內透過水溶液導入管66而適當 地供應檸檬酸水溶液。 在容器60內，係具備包含1個以上的棚架68之鎂收容 手段70，在收容手段70的棚架68上載置多數個鎂72的塊體 -21 - 201210934 。亦即，在收容手段7G中收容多數個鎂72的塊體。鎂72的 塊體’例如是指直徑4〜5mm左右以上的大小者。要讓氫氣 產生的情況，是設定成將鎂72的塊體配置在比容器60內的 液面74更下方。該收容手段70，藉由從主體62將蓋體64卸 下’可相對於容器60自由地取出放入。在棚架68上，形成 有多數個讓水能上下通過的小孔（未圖示）。棚架6 8是使 用衝孔板’其形成有多數個網眼小的網孔或是小孔。棚架 68所載置之鎂72的塊體大小，是比棚架68上所形成之小孔 更大。 鎂’除了塊體以外，也能使用小顆粒或粉末。在使用 鎂的小顆粒或粉末的情況，是使用形成有直徑非常小的多 數個孔之網製或金屬製的小型容器形狀（比容器60更小） 的收容手段75 (第6圖）。在收容手段75內放入小顆粒或 粉末狀的鎂，將該收容手段75置入容器60內。收容手段75 上所形成之小直徑的多數個孔的大小設定成，能讓水朝收 容手段75的內外進行移動，但無法讓鎂的小顆粒或粉末輕 易地通過該孔。又在該收容手段75中，亦可放入鎂的塊體 。當在內部收容有鎂之收容手段75置入容器60內的情況， 是設定成使收容手段75內的鎂位於液面74的下方。本發明 所使用的鎂，可採用市售之任意業者所提供之任意種類者Cl + e'-^Cl' (4) The Cr and Na+ produced by the ion exchange resin 32 are in a stable state in the form of ions. Further, the water after passing through the ion exchange resin 3 2 may also contain no Na + . In the water passing through the ion exchange resin 32, H+, OH_, and ion (H30+) are present as shown by the above formula (1)(2). The following reaction is produced by ion exchange of water after the resin 3 2 and then by passing through the rock 54. 0Η· + Η + ->Η20 ...(5 ) Η2〇+ Η + ^Η3〇+ · · ( 2 ) 2H + + 2e'-^2H2- (6) In this reaction, compared to ion exchange The amount of resin 32 produced, -18-201210934 will produce a larger amount of cerium ions (H3 〇) ° As explained above, by passing the rock 54 after the ion exchange resin 32, there will be in the water: Some of Na+, 〇『, newly produced C1·, ion (H3〇+) °, and the redox potential of water after passing through rock 54 become _20~-240mV. If hot water is used instead of water, the negative oxidation-reduction potential becomes more stable. Further, the water after passing through the rock 54 contains a large amount of dissolved oxygen and active hydrogen. The water passing through the rock 54 is then passed through the inside of the ion generator 14 in which the tourmaline 46 and the metal 48 are contained. Thereby the following reaction is produced. H2〇-^H + + OH'··· ( 1 ) Η20 + Η + — Η30+... ( 2 ) The ion (h3o+) is produced in large quantities. A part of the ion (H30+) becomes a hydroxyl ion (Her). H30 + + H20-»H302 +2H+... (3) As a result, the amount of ions (H30+), hydroxyl ions (Η302·), 〇H·, H + in the water after tourmaline 46 and metal 48 will pass. increase. As shown in Fig. 4, the water after passing through the ion exchange resin 32, the rock 54, and the tourmaline 46 (or a mixture of the tourmaline 46 and the metal 48) contains Na+, Cl·, ΟΗ·, and ions (Η30+). ), hydroxyl ions (Η302·), Η+, active hydrogen, and dissolved oxygen are the same components as the generated water produced in Fig. 1 . The water has an electromagnetic wave having a wavelength of 4 to 14 // m at an energy of 4 watts/cm 2 and having an oxidation-reduction potential of -20 to 24 〇 mV. As a result, the water produced in Fig. 4 has the same effect as the generated water produced in Fig. 1. The water produced by the apparatus according to Fig. 4 has the same composition as that of the creation water produced in Fig. 1-19-201210934, so the water produced by the apparatus of Fig. 4 is also the creation water. The water quality inspection results of the created water are shown below. The number of tap water compared to the water of creation is represented by brackets. If the number of tap water and created water is the same, it is marked as “identical”. Nitrous acid nitrogen and nitrate nitrogen: 1.8mg/l (same), chloride ion: 6.8mg/l (9_Omg/l), general bacteria: one /ml (same), cyanide ion: not up to 〇.〇1 Mg/1 (same), mercury: less than 0.0005 mg/1 (same), organic phosphorus: less than 〇.1 mg/1 (same), copper: less than 0.01 mg/1 (same), iron: not 0.05 mg/1 (less than 0.08 mg/1), manganese: less than 〇.〇1 mg/1 (identical), zinc: less than 0.005 mg/1 (less than 0.054 mg/1), lead: less than 0.01 Mg/1 (identical), hexavalent chromium: less than 0.02 mg/1 (same), cadmium: less than 0.005 mg/1 (same), arsenic: less than 0.005 mg/1 (same), fluorine: not up to 〇 .15mg/l (same), calcium, magnesium, etc. (hardness): 1.2mg/l (49.0 mg/1), phenols: less than 0.005 mg/1 (same), anionic surfactant: less than 0.2 mg/ 1 (same), pH値: 6.9 (same), odor: no odor (same), taste: no odor (same), chroma: 2 degrees (same), turbidity: twist (1 degree). Chuangsheng water has many of the features listed below. (a) Containing ions (H30+), hydroxyl ions (h3〇2_), hydrogen ions (H+), hydrogen, hydroxyl groups (OH_), sulfate ions (S〇4>), hydrogen carbonate ions (HC03_), carbonate ions ( CO/—), formazanic acid (H2Si03), free carbon dioxide (C02). (b) Interfacial activity -20- 201210934 Interfacial activity (OW type emulsification). (C) Has weak energy (breeding light) The tourmaline emits weak energy (electromagnetic waves with a wavelength of 4 to 14/zm). This weak energy cuts off large clusters of water and discharges toxic gases and heavy metals in the clusters to the outside of the water. (d) has an oxidation-reduction potential of -20 to -24 0 mV. (e) Contains dissolved oxygen and active hydrogen. (f) is soft water after removing calcium ions and magnesium ions. The tap water or the like is passed through an ion exchange resin to remove calcium ions and magnesium ions contained in the water. (g) Contains active hydrogencarbonate (HCOT) and formamidine (H2Si03). Next, a method for producing hydrogen gas according to the present invention will be described based on Fig. 5. The hydrogen production method of the present invention is to produce hydrogen gas using water, citric acid or magnesium. In the method for producing hydrogen gas according to the present invention, a container 60 for accommodating water, citric acid or magnesium therein is used. The container 60 is composed of a main body 62 and a lid 64 thereof. As the material of the container 60, for example, materials of various containers used in homes such as glass and metal can be used. That is, in the present invention, since the inside of the container 60 is not high pressure, the container 60 does not need to use a special material. The container 60 is provided with an aqueous solution introduction tube 66 for supplying an aqueous citric acid solution from the outside toward the inside, and an aqueous solution of citric acid can be appropriately supplied from the outside into the container 60 through the aqueous solution introduction tube 66. In the container 60, a magnesium storage means 70 including one or more scaffolds 68 is provided, and a plurality of blocks 72 of -21 - 201210934 are placed on the scaffolding 68 of the storage means 70. That is, a plurality of blocks of magnesium 72 are accommodated in the housing means 7G. The block " of magnesium 72" is, for example, a size of about 4 to 5 mm in diameter. The case where hydrogen gas is generated is set such that the block of magnesium 72 is disposed below the liquid level 74 in the container 60. The accommodating means 70 can be freely taken out from the container 60 by being detached from the main body 62. On the scaffolding 68, a plurality of small holes (not shown) for allowing water to pass up and down are formed. The scaffolding 6 8 is a perforated plate which is formed with a plurality of meshes or small holes. The block size of the magnesium 72 contained in the scaffolding 68 is larger than the small hole formed in the scaffolding 68. Magnesium 'in addition to the bulk, small particles or powders can also be used. In the case of using small particles or powder of magnesium, a storage means 75 (Fig. 6) of a small container shape (smaller than the container 60) formed of a mesh or a metal having a very small diameter is formed. Small particles or powdered magnesium are placed in the storage means 75, and the storage means 75 is placed in the container 60. The plurality of holes having a small diameter formed in the accommodating means 75 are sized to allow the water to move toward the inside and the outside of the accommodating means 75, but the small particles or powder of magnesium cannot be easily passed through the holes. Further, in the storage means 75, a block of magnesium may be placed. When the magnesium storage means 75 is housed in the container 60, the magnesium in the storage means 75 is set below the liquid level 74. The magnesium used in the present invention may be any of those available from any commercially available supplier.
Q 在蓋體64的上端安裝帽蓋76。在該帽蓋76安裝氣體取 出用嘴80，在該氣體取出用嘴80的內部形成有讓容器60的 內部和外部連通之連絡通路78。在氣體取出用嘴80的中途 -22- 201210934 設置：爲了將容器60內所產生的氫氣往外部取出而使連絡 通路78進行開閉之開閉閥82。藉由具有帽蓋76之蓋體64將 主體62的上部開口部封閉，並在將開閉閥82關閉的狀態下 ，使容器60的內部成爲密閉狀態。在容器60上，在主體62 的上部或是蓋體64安裝：用來測定容器60內部的氣壓之氣 壓計84、以及用來測定容器60內部的溫度之溫度計86。蓋 體64的形狀較佳爲，朝向上方的中央（帽蓋76)其水平截 面逐漸縮小之圓錐形狀或角錐形狀。如此，能使所生成之 比重輕的氫氣集中於容器60上方，而容易將氫氣從容器60 經由嘴80往外部取出。 來自氣壓計84和溫度計86之容器60內的壓力、溫度， 被輸入電腦88。電腦88是根據容器60內的溫度、壓力進行 判斷，爲了從容器60往外部將氫氣取出而使開閉閥82動作 。在氣體取出用嘴80的外部側的前端可具備：用來測定從 容器60往外部取出的氫氣量之氫氣量檢測裝置90。 在蓋體64的背面，設置藉由電腦88來操作之滑輪等的 昇降手段92，該昇降手段92和收容手段70，75是藉由金屬 線（wire )等的連結手段94予以連結。 昇降手段92能讓收容手段7〇，75上昇或下降，而使收 容手段70，75內所收容的鎂72浸漬在液面74的下方，或抬 高至液面74的上方。又在第5圖所示的容器60’雖是在蓋 體64設置昇降手段92 ’但在主體62—體地形成上部頂棚， 而在該主體62的上部頂棚安裝昇降手段92亦可。在此情況 ，蓋體是安裝在主體62的側面。在容器60的下方’安裝用 -23- 201210934 來將容器60內的水（檸檬酸水溶液）往外部排出之排出管 96，在排出管96的中途配備開閉閥98。 本發明是在容器60內放入水、檸檬酸以及鎂，在容器 60內將水和檸檬酸混合成檸檬酸水溶液。水和檸檬酸可在 加入容器60前事先混合，而以檸檬酸水溶液的形式加入容 器60內。在容器60內，利用水、檸檬酸、以及鎂產生反應 熱，而使容器60內的檸檬酸水溶液溫度上昇。在此，針對 本發明所使用的水，使用創生水、自來水、含氫水（水中 含有例如〇.2ppm氫氣之水）、天然水、純水這五種水進行 實驗。作爲創生水的原料之水和自來水，是使用日本長野 縣上田市的自來水。 首先說明水、檸檬酸、鎂的重量。若加入容器60內之 水的重量爲100重量份（例如100g)，則加入容器60之鎂 72重量爲1重量份（例如lg )以上。如果加入容器60的鎂 72重量未達1重量的話，氫氣產生量變得極少，而不具實 用性。鎂72的最佳重量範圍是10重量份（例如10g)以上〜 鎂無法溶於水之重量份。鎂72未達10重量份的話，氫氣產 生量會比最大氫氣產生量少。鎂72超過3 0重量份的情況， 氫氣產生量不會比3 0重量份的情況更多但鎂成本增高且鎂 變得難溶於水，因此鎂宜爲10重量份〜30重量份。 其次，針對使用水、檸檬酸及鎂在什麼溫度下能產生 多久時間的氫氣，顯示於第7圖，第8圖，第9圖，第11圖 。第7圖，第8圖，第9圖，第11圖，是將加入容器60內的 水重量（100重量份）和鎂重量（20重量份）設定成固定 -24- 201210934 量，將檸檬酸重量改變成5重量份、10重量份、20重量份 、3 0重量份的情況下，顯示容器60內的溫度變化圖表。這 時，水是分成創生水、自來水、含氫水、天然水、純水這 五種進行實驗。進行第7圖，第8圖，第9圖’第11圖的實 驗時實驗室內的溫度爲15 °C。 第7圖係顯示，在容器60內加入100重量份的水' 20重 量份的鎂、5重量份的檸檬酸的情況，容器60內的反應熱 所造成的溫度變化圖表。從水和檸檬酸和鎂混合後之反應 開始（實驗開始）起算1〇分鐘內，容器60內的水（檸檬酸 水溶液）溫度，不管是哪一種的水都會因反應熱而逐漸上 昇。從反應開始起經過1 〇分鐘後，容器60內的水（檸檬酸 水溶液）溫度到達峰値溫度之26°C~34°C (五種水的最低溫 度和最高溫度的範圍），之後，迄反應開始起經過約3 0分 鐘後，於26°C〜34°C的溫度範圍穩定地保持，然後結束氫氣 的產生反應。創生水、自來水、含氫水、天然水、純水這 五種水的反應溫度，稍有不同，有大致8 °C左右的溫度差 。但不管是使用這五種中的哪種水，溫度差（氫氣產生量 的差）不會有太大的差異。氫氣產生時間結束，是因爲經 由反應而使檸檬酸用完。在第7圖，檸檬酸爲5重量份，容 器60內的溫度爲26°C〜34°C的溫度（比室內氣溫高l〇°C)， 因此可知有氫氣產生。其產生量，相較於後述檸檬酸的重 量爲10重量份、20重量份、30重量份的情況，是較少的。 又檸檬酸未達5重量份的情況，氫氣產生量變得極少。 第8圖，是在容器60內加入100重量份的水、2〇重量份 -25- 201210934 的鎂、以及ι〇重量份的檸檬酸。在第8圖，從反應開始起 經過1 〇分鐘，容器60內的水（檸檬酸水溶液）溫度，到達 峰値溫度之52°C〜62t (五種水的最低溫度和最高溫度的範 圍），之後，從反應開始起10分鐘後至20分鐘後的約10分 鐘期間，於峰値溫度之52°C〜62°C穩定地保持。創生水、自 來水、含氫水、天然水、純水這五種水，雖然溫度有若干 變動，但該溫度的變動範圍爲1 0°C左右。反應開始起經過 2 0分鐘後起算約15分鐘內，最初溫度會下降若干，之後五 種水都保持50 °C〜5 5 °C的範圍而產生氫氣，之後停止產生氫 氣。第8圖所示之10重量份的檸檬酸，反應熱以50°C〜62°C 的範圍變遷達約20分鐘以上，因此相較於反應熱以約 26°C〜34°C以上變遷之5重量份的檸檬酸（第7圖）的情況， 可大量地產生氫氣。 第9圖，是在容器60內加入100重量份的水、20重量份 的鎂、以及20重量份的檸檬酸。第9圖，從反應開始起算 1〇分鐘後容器60內的溫度因反應熱而急劇上昇，從反應開 始起經過10分鐘至經過30分鐘後，容器60內的水（檸檬酸 水溶液）到達峰値溫度之約7.1 °C~7 9 °C (五種水的最低溫度 和最局溫度的範圍），之後，即使溫度降低，從反應開始 起經過30分鐘後仍保持約67°C〜72°C的範圍。亦即，檸檬酸 爲20重量份的情況，峰値溫度昇高至約7i°C~79°C，而且接 近峰値溫度的溫度之穩定時間變長（約2 0分鐘）。創生水 、自來水、含氫水、天然水、純水這五種水，雖峰値溫度 有若干變動，但該溫度的變動範圍爲8 °C左右。第9圖所示 -26- 201210934 之20重量份的檸檬酸，由於反應熱以約70 °C以上變遷’相 較於反應熱以約50 t以上變遷之第8圖所示的1〇重量份的 檸檬酸，可產生更大量的氫氣。 在此，第10圖係顯示’使用iOO重量份的水' 20重量 份的鎂、20重量份的檸檬酸，可產生多少氫氣之實驗結果 〇 爲了讓氫氣產生量具有客觀性，是委託第三者進行測 定分析。實驗分析結果之測定分析成績書如第1 0圖所示° 該測定分析成績書，是由位於日本長野縣佐久郡立科町蘆 田1 8 3 5之株式會社信濃公害硏究所（電話0267-56-2 1 89 ) 於2010年4月.14日所作成的。實驗的水是使用創生水100“ ，加入15g鎂及20g檸檬酸。實驗結果’ 15g鎂可獲得50升 的氫氣，因此每lg鎂可獲得3.3升的氫氣。 第1 1圖，是在容器60內加入100重量份的水、20重量 份的鎂、以及30重量份的檸檬酸。第11圖，反應開始起1〇 分鐘後容器60內的溫度急劇上昇，從反應開始起經過10分 鐘後至經過20分鐘後，容器60內的水（檸檬酸水溶液）溫 度，到達峰値溫度之約9 1 °C ~ 9 5 °C (五種水的最低溫度和最 高溫度的範圍），於該溫度範圍穩定地保持約8分鐘。之 後，容器60內的水溫度隨著時間經過而朝向60°C逐漸下降 ，反應開始起約35分鐘後~約39分鐘後成爲約60 °C’氫氣 停止產生。 第1 1圖所示之30重量份的檸檬酸的情況，穩定的峰値 溫度時間爲約8分鐘’之後，到氫氣停止產生爲止的期間 -27- 201210934 ，容器60內的水溫度逐漸下降。該第11圖的30重量份的檸 檬酸的情況，容器60內的溫度成爲70 °C以下，是從反應開 始起28分鐘後至31分鐘後的期間，之後容器60內的溫度依 序下降。相對於此，第9圖所示之20重量份的檸檬酸的情 況，縱使反應開始起30分鐘後仍保持7〇°C。在第9圖，雖 未顯示經過30分鐘後以後的溫度，但根據曲線的傾向，可 推定經過30分鐘後以後仍能保持相同溫度。第1 1圖所示之 30重量份的檸檬酸的情況，由於反應熱以約95 °C〜60 °C變遷 ，相較於反應熱以約70t以上變遷之第9圖所示的20重量 份的檸檬酸，可產生毫不遜色的氫氣量。氫氣的產生量， 在30重量份的檸檬酸的情況，相較於2〇重量份的檸檬酸的 情況下鎂每1重量份可產生約3.3升，是相同或稍多。 將第9圖與第11圖進行比較可知，在檸檬酸20重量份 的情況，容器60內的峰値溫度能以接近大致一定的溫度長 期變遷，在檸檬酸3 0重量份的的情況，容器60內的峰値溫 度，雖比檸檬酸20重量份的情況更高，但該峰値溫度的期 間短，峰値溫度之後溫度逐漸降低，而使溫度變成比檸檬 酸20重量份的情況更低。如此，要長期間產生氫氣的情況 ，檸檬酸20重量份的氫氣產生量與檸檬酸30重量份的氫氣 產生量是接近的。此外，若檸檬酸爲30重量份以上，峰値 溫度的期間比檸檬酸30重量份的情況短，因此檸檬酸30重 量份與檸檬酸3 0重量份以上，兩者的氫氣產生量接近。 本發明所使用的水，除了前述創生水以外，也能使用 純水、蒸餾水、自來水、天然水等之任意種類的水。除了 -28- 201210934 第1 1圖所示之30重量份的檸檬酸的曲線途中（反應開始起 26分鐘後~29分鐘後）以外，第7圖~第9圖之所有的反應區 域，當水是使用創生水的情況，相較於使用其他四種水的 情況，容器60內的溫度更高。基於此可知，作爲水是使用 創生水時，比起其他水可獲得更大量的氫氣。 在本發明，若容器6〇內的檸檬酸減少，氫氣產生量會 變少。在此情況，是從水溶液導入管66將檸檬酸水溶液供 應至容器60內。如此，容器60內的鎂會和檸檬酸水溶液反 應，而再度產生大量的氫氣。若在容器60內還有鎂，藉由 供應檸檬酸水溶液，可繼續產生氫氣。從水溶液導入管66 朝容器60內供應3〜4次檸檬酸水溶液時，檸檬酸鎂會以殘 留物的形式堆積在容器60底部。隨著檸檬酸鎂之堆積，鎂 會減少而使氫氣產生量減少。藉由從容器60內將殘留物除 去，能從水、檸檬酸及鎂而再度產生氫氣。 在第7圖，第8圖，第9圖，第11圖，是在反應開始起 經過30分鐘的時點結束實驗。因此，關於哪一種水的氫氣 產生持續時間較長，根據第7圖，第8圖，第9圖，第11圖 無法明確地得知。因此，使用創生水、自來水、純水、含 氫水這四種水，哪種水的氫氣產生量較多（氫氣產生的持 續時間長）之實驗結果如第12圖所示。在第12圖中，框內 的數値表示容器60內的溫度（°C)。根據第12圖的實驗可 知，從水溶液導入管66將檸檬酸水溶液供應至容器60內之 供給時間的結果。最初在容器6〇內加入水400cc (以400cc 爲100重量份）、檸檬酸20% ( 400x20°/〇 = 80g，20重量份） -29- 201210934 +碳酸鈉3% ( 40〇x3%=12g ’ 3重量份）、以及鎂80g ( 20重 量份），進行反應。之後，從水溶液導入管將檸檬酸濃 度30 %的檸檬酸水溶液追加供應至容器6〇內。 第12圖的實驗，當容器60內的溫度下降時（例如，每 隔5分鐘的時間進行測定，當溫度成爲70 °C左右時），將 檸檬酸濃度30%的檸檬酸水溶液追加供應至容器60內。創 生水、自來水、純水、含氫水這四種水當中，當使用自來 水和純水的情況，從反應開始經過25分鐘後，對容器60內 供應檸檬酸水溶液。當使用含氫水的情況，從反應開始經 過3 0分鐘，對容器60內供應檸檬酸水溶液。在使用創生水 的情況，從反應開始經過35分鐘後對容器60內供應檸檬酸 水溶液。在從反應開始經過7 〇分鐘的時點，在純水、自來 水、含氫水的情況，是供應3次檸檬酸水溶液，創生水則 是2次。再者，在從反應開始經過80分鐘的時點也是，在 創生水的情況，檸檬酸水溶液的供應仍只有2次。再者， 不管在哪個時間，創生水相較於自來水、純水、含氫水， 其容器6 0內的溫度都比其他三種水的溫度更高。如此可知 ，創生水比起自來水、純水、含氫水，氫氣的產生持續時 間更長。 在本發明，在氫氣產生後之容器60底部，以殘留物的 形式堆積著檸檬酸鎂。檸檬酸鎂可作爲醫療用藥剤、保健 食品的材料來使用，相較於習知技術的氫氣產生方法所生 成之殘留物（氧化鋁）必須廢棄，本發明的殘留物也能有 效地利用。 -30- 201210934 接下來說明要讓氫氣的產生中途停止的情況。第5圖 所示之收容手段7〇所收容之鎂的塊體、第6圖的收容手段 75內部所收容之鎂的小顆粒、粉末都是’在產生氫氣的情 況，是浸漬於液面74下方。藉此’利用鎂72與檸檬酸水溶 液的反應，而在容器60內產生氫氣。之後，在氫氣產生中 途要停止讓氫氣產生的情況，是讓昇降手段92動作而使收 容手段70，75上昇，將鎂72移動至液面74上方》結果，讓 鎂72無法與檸檬酸水溶液接觸，而能立刻停止讓氫氣產生 〇 之後，要再度產生氫氣的情況，是讓昇降手段92動作 而使收容手段70，75下降，讓棚架68上的鎂72移動至液面 74下方，而使鎂72與檸檬酸水溶液接觸。如此般，藉由讓 鎂72移動至液面74上方或液面74下方，可瞬間進行氫氣的 產生或停止讓氫氣產生，能使氫氣作爲能源的應用範圍變 廣。 作爲讓氫氣產生中途停止之其他方法，可從安裝於容 器60下方之排出管96將容器60內的檸檬酸水溶液往外部排 出。之後，要再度產生氫氣的情況，是從水溶液導入管66 導入檸檬酸水溶液。 關於鎂72，不管是「塊體」、「粉末」都能使用。一 般而言，顆粒、粉末’相較於塊體其與水的接觸表面積較 多’因此被認爲氫氣產生量較多。但在本發明，由於檸檬 酸可阻止在鎂72表面生成被覆膜，鎂72不管是「塊體」或 「粉末」皆可，其氫氣產生量並不會改變。 -31 - 201210934 【圖式簡單說明】 第1圖係顯示本發明的氫氣之製造方法所使用之特殊 水（創生水）的製造裝置一例之構造圖。 第2圖係第1圖的製造裝置所使用的水生成器之截面圖 〇 第3圖係第1圖的製造裝置所使用的離子生成器之主要 部分截面圖。 第4圖係顯示本發明的氫氣之製造方法所使用的特殊 水（創生水）之製造裝置其他例的構造圖。 第5圖係顯示讓本發明的氫氣產生的裝置之一實施例 的截面圖。 第6圖係與第5圖的裝置所使用的收容手段不同的收容 手段之立體圖。 第7圖係對於100重量份的水和20重量份的鎂，加入5 重量份的檸檬酸的情況下之各種水的水溫度之圖表。 第8圖係對於100重量份的水和20重量份的鎂，加入10 重量份的檸檬酸的情況下之各種水的水溫度之圖表。 第9圖係對於100重量份的水和20重量份的鎂，加入20 重量份的檸檬酸的情況下之各種水的水溫度之圖表。 第1〇圖是使用1〇〇重量份的水、15重量份的鎂以及20 重量份的檸檬酸所生成的氫氣產生量之測定分析成績書。 第11圖係對於100重量份的水和20重量份的鎂，加入 30重量份的檸檬酸的情況下之各種水的水溫度之圖表。 -32- 201210934 第1 2圖是顯示，在創生水、自來水、純水、含氫水這 四種水中，哪種水的氫氣產生時間較長的表。 【主要元件符號說明】 1 〇 :第1軟水生成器 12 :第2軟水生成器 14 :離子生成器 1 6 :岩石收納器 32 :離子交換樹脂 46 :電氣石 48 :金屬 54 :岩石 60 :容器 62 :主體 64 :蓋 6 6 :水溶液導入管 68 :棚架 70 :收容手段 72 :鎂 75 :收容手段 92 :昇降手段 96 :排出管 -33-Q A cap 76 is attached to the upper end of the cover 64. A gas take-out nozzle 80 is attached to the cap 76, and a communication passage 78 for allowing the inside and the outside of the container 60 to communicate with each other is formed inside the gas take-out nozzle 80. In the middle of the gas take-out nozzles -22-201210934, an opening and closing valve 82 for opening and closing the communication passage 78 for taking out the hydrogen gas generated in the container 60 to the outside is provided. The upper opening of the main body 62 is closed by the lid body 64 having the cap 76, and the inside of the container 60 is sealed in a state where the opening and closing valve 82 is closed. On the container 60, an air pressure gauge 84 for measuring the air pressure inside the container 60 and a thermometer 86 for measuring the temperature inside the container 60 are attached to the upper portion of the main body 62 or the lid 64. The shape of the cover body 64 is preferably a conical shape or a pyramid shape in which the horizontal direction of the upper center (cap 76) is gradually reduced. Thus, the generated hydrogen gas having a light specific gravity can be concentrated above the vessel 60, and the hydrogen gas can be easily taken out from the vessel 60 through the nozzle 80 to the outside. The pressure and temperature in the container 60 from the barometer 84 and the thermometer 86 are input to the computer 88. The computer 88 is judged based on the temperature and pressure in the container 60, and the opening and closing valve 82 is operated to take out hydrogen gas from the container 60 to the outside. The front end on the outer side of the gas take-out nozzle 80 may include a hydrogen gas amount detecting device 90 for measuring the amount of hydrogen gas taken out from the container 60 to the outside. On the back surface of the lid body 64, a lifting means 92 such as a pulley operated by a computer 88 is provided, and the lifting means 92 and the housing means 70, 75 are connected by a connecting means 94 such as a wire. The lifting means 92 allows the storage means 7A, 75 to be raised or lowered, and the magnesium 72 contained in the containing means 70, 75 is immersed below the liquid level 74 or raised above the liquid level 74. Further, in the container 60' shown in Fig. 5, the lifting means 92' is provided in the lid 64, but the upper ceiling is integrally formed in the main body 62, and the lifting means 92 may be attached to the upper portion of the main body 62. In this case, the cover is mounted on the side of the main body 62. The discharge pipe 96 for discharging the water (aqueous citric acid solution) in the container 60 to the outside is attached to the lower side of the container 60 by -23-201210934, and the opening and closing valve 98 is provided in the middle of the discharge pipe 96. In the present invention, water, citric acid and magnesium are placed in the container 60, and water and citric acid are mixed into the aqueous citric acid solution in the container 60. Water and citric acid may be mixed beforehand in the container 60 and added to the vessel 60 in the form of an aqueous citric acid solution. In the vessel 60, heat of reaction is generated by using water, citric acid, and magnesium to raise the temperature of the aqueous citric acid solution in the vessel 60. Here, the water used in the present invention is subjected to experiments using five types of water, namely, make-up water, tap water, hydrogen-containing water (water containing, for example, ppm. 2 ppm of hydrogen), natural water, and pure water. Water and tap water, which are raw materials for the creation of water, are tap water from Ueda City, Nagano Prefecture, Japan. First, the weight of water, citric acid, and magnesium will be described. If the weight of water added to the container 60 is 100 parts by weight (e.g., 100 g), the weight of the magnesium 72 added to the container 60 is 1 part by weight or more (e.g., lg) or more. If the weight of the magnesium 72 added to the vessel 60 is less than 1 by weight, the amount of hydrogen generation becomes extremely small, and it is not practical. The optimum weight range of magnesium 72 is 10 parts by weight (e.g., 10 g) or more. - Magnesium is insoluble in water. If the magnesium 72 is less than 10 parts by weight, the amount of hydrogen generated will be less than the maximum amount of hydrogen generated. In the case where the magnesium 72 exceeds 30 parts by weight, the amount of hydrogen generated is not more than 30 parts by weight, but the magnesium cost is increased and the magnesium becomes hardly soluble in water, so magnesium is preferably from 10 parts by weight to 30 parts by weight. Next, how long the hydrogen can be produced at what temperature using water, citric acid, and magnesium is shown in Fig. 7, Fig. 8, Fig. 9, and Fig. 11. Figure 7, Figure 8, Figure 9, Figure 11 is to set the weight of water (100 parts by weight) and magnesium weight (20 parts by weight) added to the container 60 to a fixed amount of -24 - 201210934, citric acid When the weight is changed to 5 parts by weight, 10 parts by weight, 20 parts by weight, and 30 parts by weight, a temperature change chart in the container 60 is displayed. At this time, water is divided into five types: creation water, tap water, hydrogen water, natural water, and pure water. The temperature in the laboratory at the experiment of Fig. 7, Fig. 8, and Fig. 9' Fig. 11 was 15 °C. Fig. 7 is a graph showing the temperature change caused by the heat of reaction in the container 60 in the case where 100 parts by weight of water '20 parts by weight of magnesium and 5 parts by weight of citric acid are added to the vessel 60. The temperature of the water (aqueous citric acid solution) in the vessel 60 from the start of the reaction after the mixing of water and citric acid and magnesium (in the beginning of the experiment), regardless of the type of water, gradually rises due to the heat of reaction. After 1 minute from the start of the reaction, the temperature of the water (aqueous citric acid solution) in the vessel 60 reaches the peak temperature of 26 ° C to 34 ° C (the range of the lowest temperature and the highest temperature of the five kinds of water), and thereafter, After about 30 minutes from the start of the reaction, it was stably maintained in a temperature range of 26 ° C to 34 ° C, and then the hydrogen generation reaction was terminated. The reaction temperatures of the five types of water, such as water, tap water, hydrogen water, natural water, and pure water, are slightly different, and there is a temperature difference of about 8 °C. However, regardless of which of the five types of water is used, the temperature difference (the difference in the amount of hydrogen generated) does not vary much. The hydrogen generation time is ended because the citric acid is used up by the reaction. In Fig. 7, the citric acid is 5 parts by weight, and the temperature in the container 60 is 26 ° C to 34 ° C (10 ° C higher than the indoor temperature), so that hydrogen gas generation is known. The amount of production is small compared to the case where the weight of citric acid described later is 10 parts by weight, 20 parts by weight, or 30 parts by weight. When the amount of citric acid is less than 5 parts by weight, the amount of hydrogen generated is extremely small. Fig. 8 is a view in which 100 parts by weight of water, 2 parts by weight of magnesium of -25 to 201210934, and 1 part by weight of citric acid are added to the container 60. In Fig. 8, the temperature of the water (aqueous citric acid solution) in the vessel 60 reaches the peak temperature of 52 ° C to 62 t (the range of the lowest temperature and the highest temperature of the five kinds of water) after 1 minute from the start of the reaction. Thereafter, it was stably maintained at a temperature of 52 ° C to 62 ° C from 10 minutes after the start of the reaction to about 10 minutes after 20 minutes. The five types of water, such as water, water, hydrogen, natural water and pure water, vary slightly in temperature, but the temperature ranges from around 10 °C. The initial temperature drops by a certain amount within about 15 minutes after the start of the reaction for 20 minutes, and then the five kinds of water are kept in the range of 50 ° C to 5 5 ° C to generate hydrogen gas, and then hydrogen generation is stopped. 10 parts by weight of citric acid shown in Fig. 8, the reaction heat changes in the range of 50 ° C to 62 ° C for about 20 minutes or more, and thus changes from about 26 ° C to 34 ° C or more compared to the heat of reaction. In the case of 5 parts by weight of citric acid (Fig. 7), hydrogen gas can be produced in a large amount. Fig. 9 is a view in which 100 parts by weight of water, 20 parts by weight of magnesium, and 20 parts by weight of citric acid are added to the vessel 60. In Fig. 9, the temperature in the vessel 60 rises sharply due to the reaction heat after 1 minute from the start of the reaction, and the water (aqueous citric acid solution) in the vessel 60 reaches the peak after 10 minutes from the start of the reaction to 30 minutes. The temperature is about 7.1 ° C ~ 7 9 ° C (the range of the lowest temperature and the most local temperature of the five kinds of water), after which, even if the temperature is lowered, it remains at about 67 ° C ~ 72 ° C after 30 minutes from the start of the reaction. The scope. That is, in the case where the citric acid is 20 parts by weight, the peak temperature is raised to about 7i ° C to 79 ° C, and the stabilization time of the temperature near the peak temperature becomes long (about 20 minutes). The five kinds of water, such as water, tap water, hydrogen water, natural water and pure water, have some variations in peak temperature, but the temperature range is about 8 °C. Figure 9 shows that 20 parts by weight of citric acid from -26 to 201210934 is changed by about 70 °C due to the heat of reaction, and 1 part by weight, as shown in Fig. 8 of the reaction heat of about 50 t or more. Citric acid produces a greater amount of hydrogen. Here, Fig. 10 shows the experimental results of how much hydrogen can be produced by using 20 parts by weight of water of iOO parts by weight of water, 20 parts by weight of citric acid, and in order to make the amount of hydrogen generated objective, it is commissioned third. Perform measurement analysis. The results of the analysis and analysis of the results of the analysis of the experiment are as shown in Figure 10. The analysis of the results of the analysis is based on the Shinano Public Health Research Center, located at 1 8 3 5, Asada, Sakuma-cho, Saku-gun, Nagano Prefecture, Japan. 56-2 1 89 ) Made on April 14th, 2010. The experimental water was 100% of the water used for creation, adding 15 g of magnesium and 20 g of citric acid. Experimental results '15 g of magnesium can obtain 50 liters of hydrogen, so 3.3 liters of hydrogen per lg of magnesium can be obtained. Figure 1 1 is in the container 60 parts by weight of water, 20 parts by weight of magnesium, and 30 parts by weight of citric acid were added to the inside of Fig. 11. In Fig. 11, the temperature in the vessel 60 rises sharply after 1 minute from the start of the reaction, and 10 minutes after the start of the reaction. After 20 minutes, the temperature of the water (aqueous citric acid solution) in the vessel 60 reaches the peak temperature of about 9 1 ° C to 95 ° C (the range of the lowest temperature and the highest temperature of the five kinds of water) at the temperature. The range was stably maintained for about 8 minutes. Thereafter, the temperature of the water in the vessel 60 gradually decreased toward 60 ° C as time elapsed, and after about 35 minutes from the start of the reaction to about 60 ° C after about 39 minutes, hydrogen gas ceased to be generated. In the case of 30 parts by weight of citric acid shown in Fig. 1st, the temperature of the water in the vessel 60 gradually decreased from the period -27 to 201210934 after the stable peak temperature time was about 8 minutes'. 30 parts by weight of the lemon in Fig. 11 In the case where the temperature in the container 60 is 70 ° C or lower, it is a period from 28 minutes to 31 minutes after the start of the reaction, and then the temperature in the container 60 is sequentially lowered. On the other hand, the temperature shown in Fig. 9 is 20 In the case of citric acid by weight, it is maintained at 7 ° C even after 30 minutes from the start of the reaction. In Fig. 9, although the temperature after 30 minutes has not been shown, it is estimated that after 30 minutes, according to the tendency of the curve The same temperature can be maintained in the future. In the case of 30 parts by weight of citric acid shown in Fig. 1, the heat of reaction changes from about 95 ° C to 60 ° C, and the ninth change of the reaction heat is about 70 t or more. The 20 parts by weight of citric acid shown in the figure can produce an amount of hydrogen which is not inferior to the color. The amount of hydrogen produced is 30 parts by weight of citric acid, compared with 2 parts by weight of citric acid. 1 part by weight can produce about 3.3 liters, which is the same or slightly more. Comparing Fig. 9 with Fig. 11 shows that in the case of 20 parts by weight of citric acid, the peak temperature in the container 60 can be close to a substantially constant temperature. Long-term changes in the case of 30 parts by weight of citric acid Although the peak temperature in the container 60 is higher than the case of 20 parts by weight of citric acid, the period of the peak temperature is short, and the temperature gradually decreases after the peak temperature, and the temperature becomes more than 20 parts by weight of citric acid. Therefore, in the case where hydrogen gas is generated for a long period of time, the amount of hydrogen generated by 20 parts by weight of citric acid is close to the amount of hydrogen generated by 30 parts by weight of citric acid. Further, if the citric acid is 30 parts by weight or more, the peak temperature is In the case where the amount is 30 parts by weight of citric acid, 30 parts by weight of citric acid and 30 parts by weight or more of citric acid are used, and the amount of hydrogen generated is close to each other. The water used in the present invention can be used in addition to the above-mentioned water. Any type of water such as pure water, distilled water, tap water, natural water, or the like is used. Except for the curve of 30 parts by weight of citric acid shown in Figure 1 of -28-201210934 (after 26 minutes from the start of the reaction to ~29 minutes after the start of the reaction), all the reaction areas of Figures 7 to 9 are as water. In the case of using the created water, the temperature inside the container 60 is higher than in the case of using the other four kinds of water. Based on this, it can be seen that when water is used as water, a larger amount of hydrogen can be obtained than other water. In the present invention, if the amount of citric acid in the vessel 6 is reduced, the amount of hydrogen generated is reduced. In this case, an aqueous solution of citric acid is supplied from the aqueous solution introduction pipe 66 into the container 60. Thus, the magnesium in the vessel 60 reacts with the aqueous citric acid solution to regenerate a large amount of hydrogen. If magnesium is present in the vessel 60, hydrogen can be continuously produced by supplying an aqueous solution of citric acid. When 3 to 4 aqueous citric acid solutions are supplied from the aqueous solution introduction tube 66 into the container 60, magnesium citrate is deposited as a residue on the bottom of the container 60. As the magnesium citrate is deposited, the amount of magnesium is reduced and the amount of hydrogen produced is reduced. Hydrogen can be regenerated from water, citric acid and magnesium by removing the residue from the vessel 60. In Fig. 7, Fig. 8, Fig. 9, and Fig. 11, the experiment was terminated at the time of 30 minutes from the start of the reaction. Therefore, regarding which kind of water hydrogen generation lasts for a long time, it can not be clearly known from Fig. 7, Fig. 8, Fig. 9, and Fig. 11. Therefore, the results of the experiments using Fig. 12 are shown in Fig. 12, using four types of water, such as water, tap water, pure water, and hydrogen-containing water, which have a large amount of hydrogen generated (long duration of hydrogen generation). In Fig. 12, the number 框 in the frame indicates the temperature (°C) in the container 60. According to the experiment of Fig. 12, the result of the supply time of supplying the aqueous citric acid solution into the container 60 from the aqueous solution introduction pipe 66 is known. Initially, 400 cc of water (100 parts by weight of 400 cc), 20% of citric acid (400 x 20 ° / 〇 = 80 g, 20 parts by weight) -29 - 201210934 + 3% sodium carbonate (40 〇 x 3% = 12 g) was added to the vessel 6 〇. '3 parts by weight) and 80 g (20 parts by weight) of magnesium were reacted. Thereafter, an aqueous solution of citric acid having a citric acid concentration of 30% was additionally supplied from the aqueous solution introduction tube into the container 6〇. In the experiment of Fig. 12, when the temperature in the container 60 is lowered (for example, every 5 minutes, when the temperature is about 70 °C), an aqueous citric acid solution having a citric acid concentration of 30% is additionally supplied to the container. Within 60. Among the four types of water, such as water, tap water, pure water, and hydrogen-containing water, when tap water and pure water are used, the aqueous solution of citric acid is supplied to the vessel 60 after 25 minutes from the start of the reaction. When hydrogen-containing water is used, an aqueous citric acid solution is supplied to the vessel 60 after 30 minutes from the start of the reaction. In the case of using the creation water, an aqueous citric acid solution was supplied to the vessel 60 after 35 minutes from the start of the reaction. At the time of 7 minutes from the start of the reaction, in the case of pure water, tap water, and hydrogen-containing water, the aqueous solution of citric acid was supplied three times, and the amount of the created water was two times. Further, at the time of 80 minutes from the start of the reaction, in the case of the creation of water, the supply of the aqueous citric acid solution was still only 2 times. Furthermore, no matter at which time, the temperature of the water in the container 60 is higher than that of the other three kinds of water compared to tap water, pure water and hydrogen-containing water. It can be seen that the generation of hydrogen lasts longer than that of tap water, pure water and hydrogen-containing water. In the present invention, magnesium citrate is deposited as a residue at the bottom of the vessel 60 after hydrogen generation. Magnesium citrate can be used as a material for medical use and health foods, and the residue (alumina) produced by the hydrogen generation method of the prior art must be discarded, and the residue of the present invention can be effectively utilized. -30- 201210934 Next, the case where the generation of hydrogen gas is stopped will be described. The bulk of the magnesium contained in the storage means 7 shown in Fig. 5 and the small particles and powder of magnesium contained in the storage means 75 of Fig. 6 are both immersed in the liquid surface 74 when hydrogen gas is generated. Below. Thereby, hydrogen gas is generated in the vessel 60 by the reaction of the magnesium 72 with the aqueous citric acid solution. Thereafter, in the middle of the generation of hydrogen gas, the generation of hydrogen gas is stopped, and the lifting means 92 is operated to raise the storage means 70, 75, and the magnesium 72 is moved above the liquid surface 74. As a result, the magnesium 72 cannot be contacted with the aqueous citric acid solution. After the hydrogen gas is stopped immediately, the hydrogen gas is generated again, and the lifting means 92 is operated to lower the storage means 70, 75, and the magnesium 72 on the scaffold 68 is moved below the liquid surface 74. Magnesium 72 is contacted with an aqueous citric acid solution. In this manner, by moving the magnesium 72 above the liquid surface 74 or below the liquid surface 74, hydrogen gas can be instantaneously generated or stopped to generate hydrogen gas, and the application range of hydrogen gas as an energy source can be broadened. As another method for stopping the generation of hydrogen gas, the aqueous citric acid solution in the vessel 60 can be discharged to the outside from the discharge pipe 96 attached to the lower portion of the vessel 60. Thereafter, in the case where hydrogen gas is again generated, a citric acid aqueous solution is introduced from the aqueous solution introduction pipe 66. Regarding magnesium 72, it can be used regardless of whether it is "block" or "powder". In general, the particles, powder 'have a greater contact surface area with water than the bulk' and are therefore considered to have a greater amount of hydrogen production. However, in the present invention, since citric acid prevents the formation of a coating film on the surface of magnesium 72, magnesium 72 can be used regardless of whether it is a "block" or a "powder", and the amount of hydrogen generated does not change. -31 - 201210934 [Brief Description of the Drawings] Fig. 1 is a structural view showing an example of a manufacturing apparatus of special water (created water) used in the method for producing hydrogen gas of the present invention. Fig. 2 is a cross-sectional view showing a water generator used in the manufacturing apparatus of Fig. 1 〇 Fig. 3 is a cross-sectional view showing the main part of the ion generator used in the manufacturing apparatus of Fig. 1. Fig. 4 is a structural view showing another example of a manufacturing apparatus of special water (creative water) used in the method for producing hydrogen gas of the present invention. Fig. 5 is a cross-sectional view showing an embodiment of a device for producing hydrogen gas of the present invention. Fig. 6 is a perspective view of a housing means different from the housing means used in the apparatus of Fig. 5. Fig. 7 is a graph showing the water temperatures of various waters in the case of adding 5 parts by weight of citric acid to 100 parts by weight of water and 20 parts by weight of magnesium. Fig. 8 is a graph showing the water temperatures of various waters in the case of adding 10 parts by weight of citric acid to 100 parts by weight of water and 20 parts by weight of magnesium. Fig. 9 is a graph showing the water temperatures of various waters in the case of adding 20 parts by weight of citric acid to 100 parts by weight of water and 20 parts by weight of magnesium. The first graph is a measurement analysis result of the amount of hydrogen generated by using 1 part by weight of water, 15 parts by weight of magnesium, and 20 parts by weight of citric acid. Fig. 11 is a graph showing the water temperatures of various waters in the case of adding 30 parts by weight of citric acid to 100 parts by weight of water and 20 parts by weight of magnesium. -32- 201210934 Figure 1 2 shows a table showing which water has a longer hydrogen production time in the four types of water, such as water, water, pure water and hydrogen. [Main component symbol description] 1 〇: 1st soft water generator 12: 2nd soft water generator 14: Ion generator 1 6 : Rock storage device 32: Ion exchange resin 46: Tourmaline 48: Metal 54: Rock 60: Container 62: main body 64: cover 6 6 : aqueous solution introduction pipe 68 : scaffold 70 : storage means 72 : magnesium 75 : storage means 92 : lifting means 96 : discharge pipe - 33 -