JP2016064937A - Solid-liquid separator for hydrogen generation and method for reusing catalyst for hydrogen generation - Google Patents

Solid-liquid separator for hydrogen generation and method for reusing catalyst for hydrogen generation Download PDF

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JP2016064937A
JP2016064937A JP2014193207A JP2014193207A JP2016064937A JP 2016064937 A JP2016064937 A JP 2016064937A JP 2014193207 A JP2014193207 A JP 2014193207A JP 2014193207 A JP2014193207 A JP 2014193207A JP 2016064937 A JP2016064937 A JP 2016064937A
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hydrogen generation
catalyst
solid
reactor
separator
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JP6353755B2 (en
JP2016064937A5 (en
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伸明 水木
Nobuaki Mizuki
伸明 水木
直樹 高坂
Naoki Kosaka
直樹 高坂
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TONAMI TRANSP CO Ltd
TONAMI TRANSPORTATION CO Ltd
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TONAMI TRANSPORTATION CO Ltd
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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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Abstract

PROBLEM TO BE SOLVED: To provide a device for recovering a catalyst in a hydrogen generator, and a method for recovering the same.SOLUTION: The device comprises: a reactor to which an aluminum raw material, an alkaline aqueous solution, and a catalyst for hydrogen generation are added; and a separator for solid-liquid separation of a mixture after completion of a reaction in the reactor, where the separator comprises a filter having an inclined part, and an outlet at a lower end part of the inclined part.SELECTED DRAWING: Figure 1

Description

本発明は、アルミニウム原材料を用いた水素発生技術に関し、特に水素発生に用いた触媒の回収及び再利用方法に係る。   The present invention relates to a hydrogen generation technique using an aluminum raw material, and more particularly to a method for recovering and reusing a catalyst used for hydrogen generation.

水素を発生させる方法としては、水酸化ナトリウム，水酸化カリウム等のアルカリ性水溶液にアルミニウム原材料を投入し、反応させる技術は周知である。
しかし、単にアルミをアルカリ性水溶液に投入するだけでは反応性が弱いことから、本願特許出願人は先に水素発生触媒を用いる技術を提案している（特許文献１）。
この技術に用いる触媒は、比較的高価であることから再利用できることが要求されていた。 As a method for generating hydrogen, a technique in which an aluminum raw material is charged into an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide and reacted is well known.
However, since the reactivity is weak simply by putting aluminum into an alkaline aqueous solution, the present applicant has previously proposed a technique using a hydrogen generation catalyst (Patent Document 1).
The catalyst used in this technique is required to be reusable because it is relatively expensive.

特開２０１４−８８２８０号公報JP 2014-88280 A

本発明は、水素発生装置における触媒の回収装置及びその回収方法の提供を目的とする。   An object of the present invention is to provide a catalyst recovery device and a recovery method thereof in a hydrogen generator.

本発明に係る水素発生用固液分離装置は、アルミニウム原材料，アルカリ性水溶液及び水素発生触媒を投入する反応器と、前記反応器で反応終了後の混合液を固液分離する分離器を備え、前記分離器は傾斜部を有するフィルターと、当該傾斜部の下端部に取出口とを有することを特徴とする。
また、本発明に係る水素発生触媒の再利用方法は、請求項１記載の水素発生用固液分離装置を用いて分離回収した溶液分を前記反応器に再投入することを特徴とする。 A solid-liquid separation device for hydrogen generation according to the present invention comprises a reactor into which an aluminum raw material, an alkaline aqueous solution and a hydrogen generation catalyst are charged, and a separator for solid-liquid separation of a mixed liquid after completion of the reaction in the reactor, The separator includes a filter having an inclined portion and an outlet at a lower end portion of the inclined portion.
The method for reusing a hydrogen generating catalyst according to the present invention is characterized in that the solution separated and recovered by using the solid-liquid separator for hydrogen generation according to claim 1 is reintroduced into the reactor.

本発明に係る水素発生触媒は、アルカリ性水溶液に溶解する塩を用いた点に特徴がある。
溶解性塩としては、Ｆｅ２（ＳＯ４）３，ＦｅＣｌ３，Ｆｅ（ＮＨ４）（ＳＯ４）２，（ＮＨ４）２Ｆ２（ＳＯ４）２，ＭｇＣｌ２，Ａｇ３ＳＯ４，Ｃｏ（ＮＯ３）２，Ｋ２ＣＯ３，ＣｕＳＯ４，ＺｎＳＯ４，ＮａＦ，Ｎａ２ＳＯ４，Ｎａ３ＰＯ４，ＮａＣｌＯ４等が例として挙げられ、その中でもＦｅ系の塩又は／及びリン酸系の塩が好ましい。
本発明に用いる触媒は、固液分離にて溶液側に回収される。 The hydrogen generation catalyst according to the present invention is characterized in that a salt that dissolves in an alkaline aqueous solution is used.
Soluble salts include Fe 2 (SO 4 ) 3 , FeCl 3 , Fe (NH 4 ) (SO 4 ) 2 , (NH 4 ) 2 F 2 (SO 4 ) 2 , MgCl 2 , Ag 3 SO 4 , Co (NO 3 ) 2 , K 2 CO 3 , CuSO 4 , ZnSO 4 , NaF, Na 2 SO 4 , Na 3 PO 4 , NaClO 4, etc. are mentioned as examples, among which Fe-based salts or / and phosphoric acid-based materials The salt of is preferred.
The catalyst used in the present invention is recovered on the solution side by solid-liquid separation.

アルミニウム原材料をアルカリ性水溶液と反応させると、コロイド状のアルミン酸塩が副生成物として発生する。
このような状態の反応終了混合液を傾斜部を有するフィルター上に投下する。
するとコロイド状の副生成物は、フィルターの傾斜部に沿って下降する。
この下降時に溶液分はフィルターの目を通して、下側に回収され、固形分は取出口から回収される。
触媒の量としては極かでよいが、溶液中の濃度としては０．００１〜０．１モル／リットルの範囲でよく、好ましくは０．００５〜０．０１モル／リットルの範囲である。 When the aluminum raw material is reacted with an alkaline aqueous solution, colloidal aluminate is generated as a by-product.
The reaction-terminated liquid mixture in such a state is dropped on a filter having an inclined portion.
Then, the colloidal by-product descends along the inclined portion of the filter.
At the time of the descent, the solution is collected through the filter through the bottom, and the solid is collected from the outlet.
The amount of the catalyst may be extremely small, but the concentration in the solution may be in the range of 0.001 to 0.1 mol / liter, preferably in the range of 0.005 to 0.01 mol / liter.

本発明においては、水溶性の塩からなる水素発生触媒を用い、固液分離により水溶液側にこの触媒を回収したので、繰り返し再利用ができ、消耗分だけ適宜補充すればよくなり、安価な水素発生方法となる。   In the present invention, a hydrogen generating catalyst composed of a water-soluble salt is used, and this catalyst is recovered on the aqueous solution side by solid-liquid separation. Therefore, it can be reused repeatedly, and it is sufficient to replenish only the consumed amount. It becomes the generation method.

本発明に係る装置の構造例を示す。The structural example of the apparatus based on this invention is shown.

本発明に係る固液分離方法を採用した装置の構造例を図１に模式的に示す。
図１に示した例は、反応器を２基並列に設けることで交互に連続使用できるようにした例である。
第１反応器１２と第２反応器１３とが、反応液タンク１１と制御バルブ１１ａ等を介して連結されている。
第１，第２反応器１１，１２は、交互に使用できるようにバブル１２ａ，１３ａをそれぞれ有し、バルブを開きアルミニウム原材料を投入する。
反応液タンク１１には、ｐＨ１３以上のアルカリ性水溶液と、溶解性の水素発生触媒を貯留してある。
配管系の詳細は省略したが、反応液タンク側の制御側のバルブ１１ａを開くと触媒が溶解した反応液が第１反応器１２、又は第２反応器１３に注入され、水素ガスが発生する。
発生した水素ガスは、燃料電池等に供給され、発電等に利用される。
反応が終了した反応器側のバルブ（１２ｂ，１３ｂ）を開くと、反応終了間がない溶液は反応熱により５０℃以上になっていることもあり、コロイド状である。
この状態で分離器１４の上部に設けた投入口（１５ａ，１５ｂ）のうち、一方から投下する。
分離器１４の内部には、傾斜部１４ｂを有するフィルター１４ａが配置されている。
副生成物がコロイド状に発生した反応終了液をフィルター１４ａの上に投下すると、コロイド状の固形分２１は、フィルター１４ａの傾斜部１４ｂに沿って降下し、傾斜部下端部の取出口１４ｃから回収される。
フィルター１４ａの目を通過した溶液分は、ポンプアップ等により反応液タンク１１に戻される。 An example of the structure of an apparatus employing the solid-liquid separation method according to the present invention is schematically shown in FIG.
The example shown in FIG. 1 is an example in which two reactors are provided in parallel so that they can be used alternately and continuously.
The 1st reactor 12 and the 2nd reactor 13 are connected via the reaction liquid tank 11 and the control valve 11a.
The first and second reactors 11 and 12 have bubbles 12a and 13a, respectively, so that they can be used alternately, and the valves are opened to feed the aluminum raw material.
The reaction liquid tank 11 stores an alkaline aqueous solution having a pH of 13 or more and a soluble hydrogen generation catalyst.
Although details of the piping system are omitted, when the control side valve 11a on the reaction liquid tank side is opened, the reaction liquid in which the catalyst is dissolved is injected into the first reactor 12 or the second reactor 13, and hydrogen gas is generated. .
The generated hydrogen gas is supplied to a fuel cell or the like and used for power generation or the like.
When the valve (12b, 13b) on the reactor side where the reaction has been completed is opened, the solution with no reaction completion may be 50 ° C. or higher due to the reaction heat and is colloidal.
In this state, it is dropped from one of the inlets (15a, 15b) provided in the upper part of the separator.
A filter 14 a having an inclined portion 14 b is disposed inside the separator 14.
When the reaction-finished liquid in which by-products are generated in colloidal form is dropped on the filter 14a, the colloidal solid content 21 descends along the inclined part 14b of the filter 14a and passes through the outlet 14c at the lower end of the inclined part. Collected.
The solution that has passed through the eyes of the filter 14a is returned to the reaction liquid tank 11 by pumping up or the like.

本発明においては、触媒の消耗量を分析にて計測してもよく、アルカリ性のｐＨを測定し、アルカリ分の消耗を代替特性として用いてもよい。
ｐＨが所定の値以上、例えばｐＨ＝１３．５以上であれば水のみを補給し、ｐＨがそれ以下になると所定濃度に触媒を溶解したアルカリ性水溶液又はその原液を補給することで反応性を回復させることができる。 In the present invention, the amount of consumption of the catalyst may be measured by analysis, the alkaline pH may be measured, and the consumption of alkali may be used as an alternative characteristic.
If the pH is higher than a predetermined value, for example, pH = 13.5 or higher, only water is replenished, and when the pH is lower than that, the alkaline aqueous solution in which the catalyst is dissolved to a predetermined concentration or its stock solution is replenished. Can be made.

１１ 反応液タンク
１２ 第１反応器
１３ 第２反応器
１４ 分離器
１４ａ フィルター
１４ｂ 傾斜部
２１ 固形分
２２ 溶液分 DESCRIPTION OF SYMBOLS 11 Reaction liquid tank 12 1st reactor 13 2nd reactor 14 Separator 14a Filter 14b Inclination part 21 Solid content 22 Solution content

Claims (2)

アルミニウム原材料，アルカリ性水溶液及び水素発生触媒を投入する反応器と、
前記反応器で反応終了後の混合液を固液分離する分離器を備え、
前記分離器は傾斜部を有するフィルターと、当該傾斜部の下端部に取出口とを有することを特徴とする水素発生用固液分離装置。 A reactor into which aluminum raw materials, an alkaline aqueous solution and a hydrogen generation catalyst are charged;
A separator for solid-liquid separation of the mixed solution after completion of the reaction in the reactor;
The separator has a filter having an inclined portion, and an outlet at the lower end of the inclined portion. 請求項１記載の水素発生用固液分離装置を用いて分離回収した溶液分を前記反応器に再投入することを特徴とする水素発生触媒の再利用方法。   A method for reusing a hydrogen generating catalyst, wherein the solution separated and recovered using the solid-liquid separator for hydrogen generation according to claim 1 is reintroduced into the reactor.
JP2014193207A 2014-09-24 2014-09-24 Solid-liquid separator for hydrogen generation and method for reusing hydrogen generation catalyst Active JP6353755B2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018002557A (en) * 2016-07-05 2018-01-11 アルハイテック株式会社 Hydrogen production apparatus and production method using the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54170478U (en) * 1978-05-23 1979-12-01
JP2003190990A (en) * 2001-12-26 2003-07-08 Toshio Fukuda Treatment system for sewerage cleaning sludge
WO2007116734A1 (en) * 2006-03-28 2007-10-18 Mitsubishi Heavy Industries, Ltd. Energy supply system and hydrogen-generating substance
JP2009131792A (en) * 2007-11-30 2009-06-18 Chugoku Electric Power Co Inc:The Fly ash balloon recovering method and system
JP2014088280A (en) * 2012-10-30 2014-05-15 Tonami Transportation Co Ltd Hydrogen generator

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54170478U (en) * 1978-05-23 1979-12-01
JP2003190990A (en) * 2001-12-26 2003-07-08 Toshio Fukuda Treatment system for sewerage cleaning sludge
WO2007116734A1 (en) * 2006-03-28 2007-10-18 Mitsubishi Heavy Industries, Ltd. Energy supply system and hydrogen-generating substance
JP2009131792A (en) * 2007-11-30 2009-06-18 Chugoku Electric Power Co Inc:The Fly ash balloon recovering method and system
JP2014088280A (en) * 2012-10-30 2014-05-15 Tonami Transportation Co Ltd Hydrogen generator

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018002557A (en) * 2016-07-05 2018-01-11 アルハイテック株式会社 Hydrogen production apparatus and production method using the same

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