JP7423055B2 - Method for recovering alkaline aqueous solution used for hydrogen production - Google Patents
Method for recovering alkaline aqueous solution used for hydrogen production Download PDFInfo
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- JP7423055B2 JP7423055B2 JP2020055212A JP2020055212A JP7423055B2 JP 7423055 B2 JP7423055 B2 JP 7423055B2 JP 2020055212 A JP2020055212 A JP 2020055212A JP 2020055212 A JP2020055212 A JP 2020055212A JP 7423055 B2 JP7423055 B2 JP 7423055B2
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- aqueous solution
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- 239000007864 aqueous solution Substances 0.000 title claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 20
- 239000001257 hydrogen Substances 0.000 title claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000004645 aluminates Chemical class 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
Description
本発明は、アルミニウム又はアルミニウム合金（以下、必要に応じてアルミニウム合金等と称する。）と反応させて水素を製造するのに用いられるアルカリ性水溶液の回収方法に関する。 The present invention relates to a method for recovering an alkaline aqueous solution used to produce hydrogen by reacting with aluminum or an aluminum alloy (hereinafter referred to as aluminum alloy or the like as necessary).
アルミニウム合金等をｐＨ１３以上の高濃度のアルカリ性水溶液に溶解反応させることで水素が発生する。
アルカリ性水溶液としては、水酸化ナトリウム、水酸化カリウム等が用いられる。
例えば、水酸化ナトリウムにて説明する。
（１）２Ａｌ＋２ＮａＯＨ＋２Ｈ２Ｏ→２ＮａＡｌＯ２＋３Ｈ２なる反応で水素が発生し、水溶性のアルミン酸ナトリウム（ＮａＡｌＯ２）が得られる。
ＮａＡｌＯ２は、加水分解により下記のような反応が考えられる。
（２）ＮａＡｌＯ２＋Ｈ２Ｏ→Ａｌ（ＯＯＨ）＋ＮａＯＨ
（３）ＮａＡｌＯ２＋２Ｈ２Ｏ→Ａｌ（ＯＨ）３＋ＮａＯＨ
これらの反応は、結晶学的な結晶構造からなる水酸化アルミニウム結晶が生成されるものではなく、いわばゾル状の状態にある結晶性水酸化アルミニウムと水酸化ナトリウムとの混合物になるため、ＮａＯＨの水溶液が充分に回収されない技術的課題があった。
Hydrogen is generated by dissolving an aluminum alloy or the like in a highly concentrated alkaline aqueous solution with a pH of 13 or higher.
As the alkaline aqueous solution, sodium hydroxide, potassium hydroxide, etc. are used.
For example, sodium hydroxide will be explained.
(1) Hydrogen is generated by the reaction 2Al+2NaOH+2H 2 O→2NaAlO 2 +3H 2 and water-soluble sodium aluminate (NaAlO 2 ) is obtained.
When NaAlO 2 is hydrolyzed, the following reactions can be considered.
(2) NaAlO 2 +H 2 O → Al(OOH) + NaOH
(3) NaAlO 2 +2H 2 O→Al(OH) 3 +NaOH
These reactions do not produce aluminum hydroxide crystals with a crystallographic crystal structure, but instead produce a mixture of crystalline aluminum hydroxide and sodium hydroxide in a so-called sol-like state. There was a technical problem in that the aqueous solution was not sufficiently recovered.
特許文献１には、反応器から固形物を排出しながら連続的に水素を得る方法を開示するが、この固形物にはアルカリ成分が混入されているため、アルカリ成分の消耗が激しいものである。 Patent Document 1 discloses a method for continuously obtaining hydrogen while discharging solid matter from a reactor, but since this solid matter is mixed with an alkali component, the alkali component is rapidly consumed. .
本発明は、アルミニウム合金等を溶解し、水素を製造するのに用いられるアルカリ性水溶液の繰り返し使用における回収率が高いアルカリ性水溶液の回収方法の提供を目的とする。 An object of the present invention is to provide a method for recovering an alkaline aqueous solution that has a high recovery rate during repeated use of the alkaline aqueous solution used to produce hydrogen by dissolving an aluminum alloy or the like.
本発明に係るアルカリ性水溶液の回収方法は、アルミニウム又はアルミニウム合金と反応させることで水素を製造するのに用いられるアルカリ性水溶液の繰り返し使用方法であって、前記アルカリ性水溶液はアルミニウムをアルミン酸アルカリの水溶液として溶解することで水素を発生させるステップと、アルミン酸アルカリ性水溶液から冷却等により水酸化アルミニウム・アルカリ水混合析出物を析出させ固液分離することでアルカリ性水溶液の１次回収ステップと、前記水酸化アルミニウム・アルカリ水混合物からフィルタープレスにてアルカリ水の２次回収ステップとを有することを特徴とする。 The method for recovering an alkaline aqueous solution according to the present invention is a method for repeatedly using an alkaline aqueous solution used to produce hydrogen by reacting with aluminum or an aluminum alloy, wherein the alkaline aqueous solution converts aluminum into an aqueous solution of an alkali aluminate. a step of generating hydrogen by dissolving the alkaline aluminate aqueous solution; a step of primary recovery of the alkaline aqueous solution by precipitating a mixed precipitate of aluminum hydroxide and alkaline water by cooling etc. from the alkaline aluminate aqueous solution and performing solid-liquid separation; - A second recovery step of alkaline water from the alkaline water mixture using a filter press.
ここで、前記水酸化アルミニウム・アルカリ水混合物からアルカリ水を２次回収した粗水酸化アルミニウムをさらに、少量の水又は温水にて洗浄し、アルカリ成分の３次回収ステップを有するようにすると、より回収率が向上する。 Here, if the crude aluminum hydroxide obtained by secondary recovery of alkaline water from the aluminum hydroxide/alkaline water mixture is further washed with a small amount of water or hot water to have a tertiary recovery step of the alkaline component, it is even more effective. Recovery rate improves.
本発明において、前記アルカリ性水溶液は水溶性の水素発生触媒が含有されていてもよく、その場合に水素発生触媒の消耗も低減できる。 In the present invention, the alkaline aqueous solution may contain a water-soluble hydrogen generating catalyst, in which case consumption of the hydrogen generating catalyst can also be reduced.
従来、アルミン酸アルカリの水溶液から加水分解により、水酸化アルミニウムを折出させただけでは、アルカリ成分がこの水酸化アルミニウムに多く混合し、水酸化アルミニウム・アルカリ水混合物になっているため、アルカリ成分の消耗が激しく、充分に繰り返し使用できなかった。
これに対して本発明は、水酸化アルミニウム・アルカリ混合物を脱水操作することでアルカリ水の回収ができ、さらに少量の水や温水で上記固形物を洗浄しアルカリ分を回収することで、さらに回収率が向上する。
Conventionally, when aluminum hydroxide was simply precipitated by hydrolysis from an aqueous solution of alkali aluminate, a large amount of alkali components were mixed with this aluminum hydroxide, resulting in a mixture of aluminum hydroxide and alkaline water. It was severely worn out and could not be used repeatedly.
In contrast, in the present invention, alkaline water can be recovered by dehydrating the aluminum hydroxide/alkali mixture, and further recovered by washing the solid matter with a small amount of water or hot water to recover the alkaline content. rate is improved.
以下、本発明に係る回収方法を具体的に説明する。
ｐＨ１３以上の高濃度の水酸化ナトリウムの水溶液が貯留された反応タンクにアルミニウム合金を投入し、水素を製造した。
なお、反応タンクには０．００１～０．１モル／リットルの水素発生触媒を添加してある。
反応が終了すると、反応液を別の回収タンクにポンプ輸送し、液温を下げることで水酸化アルミニウム・アルカリ混合物を折出させた。
この液を濾過し、濾液をアルカリ性水溶液として１次回収した。
Hereinafter, the collection method according to the present invention will be specifically explained.
An aluminum alloy was charged into a reaction tank in which a highly concentrated aqueous solution of sodium hydroxide with a pH of 13 or higher was stored to produce hydrogen.
Note that a hydrogen generating catalyst of 0.001 to 0.1 mol/liter was added to the reaction tank.
When the reaction was completed, the reaction solution was pumped to another recovery tank, and the aluminum hydroxide/alkali mixture was precipitated by lowering the solution temperature.
This liquid was filtered, and the filtrate was primarily recovered as an alkaline aqueous solution.
上記にて得られた固形分をフィルタープレス機に投入し、含水率約８０％レベルまで脱水することでアルカリ水を２次回収し、反応タンクにリターンした。
これにより、水酸化アルミニウム・アルカリ水混合物からアルカリ成分をアルカリ水として回収できた。
脱水処理して残った粗結晶性水酸化アルミニウムには、まだアルカリ分が残っていることから、これを少量の温水で洗浄したところ、洗浄水は強いアルカリ性を示したので、これも反応タンクにリターンさせた。
なお、洗浄はフィルターに保持した固形物に少量の４０～６０℃の温水（固形分の１０～２０％の量）を上からかけるようにして、３～５回回収を繰り返した。
The solid content obtained above was put into a filter press machine and dehydrated to a water content level of about 80% to recover secondary alkaline water, which was then returned to the reaction tank.
As a result, the alkaline component could be recovered as alkaline water from the aluminum hydroxide/alkaline water mixture.
The crude crystalline aluminum hydroxide that remained after dehydration still had alkaline content, so when we washed it with a small amount of warm water, the washing water showed strong alkalinity, so we added this to the reaction tank as well. I returned it.
For washing, a small amount of 40 to 60°C warm water (10 to 20% of the solid content) was poured over the solids retained in the filter, and collection was repeated 3 to 5 times.
上記にてアルカリ性水溶液をリターン回収した反応タンクにアルミニウム合金を投入したところ、その前と同様に水素製造に供することができ、この水素製造を繰り返し行うことができた。
この場合に、水素発生触媒の減少も少なく、そのまま繰り返し使用できた。
このことは、高価な触媒の寿命も長くなり、生産性が向上する。
従来は水素の製造毎にアルカリ水や触媒を補充していたのに本発明にあっては、数回、連続的に水素製造ができ、補充する際にものと補充量が少なくなった。
When the aluminum alloy was put into the reaction tank into which the alkaline aqueous solution was returned and recovered in the above, it could be used for hydrogen production as before, and this hydrogen production could be repeated.
In this case, there was little loss of the hydrogen generating catalyst, and it could be used repeatedly as is.
This also extends the life of expensive catalysts and improves productivity.
In the past, alkaline water and catalyst were replenished each time hydrogen was produced, but with the present invention, hydrogen can be produced several times in succession, and the amount of replenishment is reduced.
Claims (1)
前記アルカリ性水溶液に、アルミニウムをアルミン酸アルカリの水溶液として溶解することで水素を発生させるステップと、
アルミン酸アルカリ性水溶液から冷却により水酸化アルミニウム・アルカリ水混合析出物を析出させ固液分離することでアルカリ性水溶液を回収する、１次回収ステップと、
前記水酸化アルミニウム・アルカリ水混合物からフィルタープレスにてアルカリ性水溶液を回収する、２次回収ステップと、
前記水酸化アルミニウム・アルカリ水混合物からアルカリ性水溶液を２次回収した粗結晶性水酸化アルミニウムをさらに、少量の水又は温水にて洗浄し、アルカリ性水溶液を回収する、３次回収ステップを有し、
前記アルカリ性水溶液は水溶性の水素発生触媒が含有されていることを特徴とする前記１次～３次回収ステップによりアルカリ性水溶液を繰り返し使用するためのアルカリ性水溶液の回収方法。 A method for recovering an alkaline aqueous solution used to produce hydrogen by reacting with aluminum or an aluminum alloy, the method comprising:
generating hydrogen by dissolving aluminum as an alkali aluminate aqueous solution in the alkaline aqueous solution;
a primary recovery step in which a mixed aluminum hydroxide/alkaline water precipitate is precipitated from the aluminate alkaline aqueous solution by cooling and the alkaline aqueous solution is recovered by solid-liquid separation;
a secondary recovery step of recovering an alkaline aqueous solution from the aluminum hydroxide/alkaline water mixture using a filter press ;
A tertiary recovery step in which the crude crystalline aluminum hydroxide obtained by secondarily recovering the alkaline aqueous solution from the aluminum hydroxide/alkaline water mixture is further washed with a small amount of water or hot water to recover the alkaline aqueous solution,
A method for recovering an alkaline aqueous solution for repeatedly using the alkaline aqueous solution in the first to tertiary recovery steps, wherein the alkaline aqueous solution contains a water-soluble hydrogen generating catalyst .
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| JP2020055212A JP7423055B2 (en) | 2020-03-26 | 2020-03-26 | Method for recovering alkaline aqueous solution used for hydrogen production |
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| JP2020055212A JP7423055B2 (en) | 2020-03-26 | 2020-03-26 | Method for recovering alkaline aqueous solution used for hydrogen production |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004210591A (en) | 2002-12-27 | 2004-07-29 | Itec Co Ltd | Apparatus and method of producing gaseous hydrogen |
| JP2008019158A (en) | 2006-06-14 | 2008-01-31 | Hiroko Ishikuri | Method for producing high purity aluminum hydroxide and high purity aluminum hydroxide obtained by the method |
| JP2010001175A (en) | 2008-06-19 | 2010-01-07 | Furukawa-Sky Aluminum Corp | Method of producing sodium aluminate and hydrogen |
| JP2014088280A (en) | 2012-10-30 | 2014-05-15 | Tonami Transportation Co Ltd | Hydrogen generator |
| US20170033382A1 (en) | 2014-04-13 | 2017-02-02 | Alcoa Inc. | Systems and methods for regeneration of aqueous alkaline solution |
| 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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- 2020-03-26 JP JP2020055212A patent/JP7423055B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004210591A (en) | 2002-12-27 | 2004-07-29 | Itec Co Ltd | Apparatus and method of producing gaseous hydrogen |
| JP2008019158A (en) | 2006-06-14 | 2008-01-31 | Hiroko Ishikuri | Method for producing high purity aluminum hydroxide and high purity aluminum hydroxide obtained by the method |
| JP2010001175A (en) | 2008-06-19 | 2010-01-07 | Furukawa-Sky Aluminum Corp | Method of producing sodium aluminate and hydrogen |
| JP2014088280A (en) | 2012-10-30 | 2014-05-15 | Tonami Transportation Co Ltd | Hydrogen generator |
| US20170033382A1 (en) | 2014-04-13 | 2017-02-02 | Alcoa Inc. | Systems and methods for regeneration of aqueous alkaline solution |
| 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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