JP2018002557A - Hydrogen production apparatus and production method using the same - Google Patents
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 37
- 239000001257 hydrogen Substances 0.000 title claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000049 pigment Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
Description
本発明は、飲料缶，食料缶等として使用後に回収されたアルミ缶を原材料に用いた水素製造装置及び製造方法に関する。 The present invention relates to a hydrogen production apparatus and production method using aluminum cans collected after use as beverage cans, food cans and the like as raw materials.
アルミニウム及びその合金を用いたタブ缶，ボトル缶等からなるアルミ缶が、飲料用，食料用あるいはその他の容器として広く使用されている。
これらのアルミ缶は、分別回収，拠点回収，集団回収等により使用後に回収され、リサイクル使用に供されている。
本発明は、これらの回収されたアルミ缶を有価物として、新たなエネルギー資源として活用すべく、本発明に至った。
Aluminum cans such as tab cans, bottle cans and the like using aluminum and its alloys are widely used for beverages, foods, and other containers.
These aluminum cans are collected after use by separate collection, base collection, group collection, etc., and are used for recycling.
The present invention has led to the present invention in order to use these recovered aluminum cans as valuable resources and as new energy resources.
特許文献１には、燃料としてアルミ粉と水を供給する水素エネルギー車両を開示し、このアルミ粉としてアルミ缶を粉砕して用いることが記載されている。
しかし、各種容器として用いられたアルミ缶は表面に印刷や塗装が施され、これらには各種顔料が用いられているので、残渣物として残る問題がある。
Patent Document 1 discloses a hydrogen energy vehicle that supplies aluminum powder and water as fuel, and describes that an aluminum can is crushed and used as the aluminum powder.
However, aluminum cans used as various containers are printed or painted on the surface, and since various pigments are used for these, there is a problem that they remain as residues.
本発明は、回収されたアルミ缶を原料に用いた水素製造装置及び製造方法の提供を目的とする。 An object of this invention is to provide the hydrogen production apparatus and manufacturing method which used the collect | recovered aluminum can as a raw material.
本発明に係る水素製造装置は、破砕された回収アルミ缶を投入するホッパー部と、アルカリ性の反応液を貯留する反応液貯留タンクと、前記破砕された回収アルミ缶と前記アルカリ性の反応液とを反応させる反応器を備え、反応器で反応終了後の反応終了液を固液分離する固液分離器を有し、前記固液分離器から得られた濾過液を前記反応液貯留タンクに返送する返送手段を有することを特徴とする。 The hydrogen production apparatus according to the present invention includes a hopper part for charging a crushed recovered aluminum can, a reaction liquid storage tank for storing an alkaline reaction liquid, the crushed recovered aluminum can and the alkaline reaction liquid. A reactor for reacting, having a solid-liquid separator for solid-liquid separation of the reaction-finished liquid after completion of the reaction in the reactor, and returning the filtrate obtained from the solid-liquid separator to the reaction liquid storage tank It has a return means.
ここで破砕された回収アルミ缶とは、使用済みのアルミ缶を回収し、破砕機にて小片状に破砕したものをいう。
使用済みのアルミ缶には、タブタイプの蓋からなるタブ缶や、キャップタイプの蓋からなるアルミボトル缶等、形態に制限はない。
回収手段には、自治体等にて行われている分別回収、店先等に回収ボックスを設けた拠点回収、子供会等の各種会、団体等による集団回収等、回収方法に制限はない。
Here, the crushed recovered aluminum can refers to a used aluminum can that has been collected and crushed into small pieces by a crusher.
The used aluminum cans are not limited in form, such as a tab can made of a tab type lid or an aluminum bottle can made of a cap type lid.
There are no limitations on the collection method for collection means, such as separate collection performed by local governments, collection of bases provided with collection boxes at storefronts, various groups such as children's associations, group collection by groups, and the like.
アルミ缶は、各種商品の容器として用いられたものであり、表面に印刷や塗装等が施されているため、本発明はアルカリ性の水溶液と反応させ、残った顔料等を固液分離器を用いて除去し、反応液を再利用できるようにした点に特徴がある。
なお、この表面の印刷層や塗装層を破砕前や後に加熱除去，乾留除去してもよく、その場合にも完全に除去できなくても残渣物は固液分離器にて除去できる。
この固液分離器は、アルカリ水溶液とアルミとの反応により生成した水酸化アルミ等の反応残渣物も除去できる。
本発明に用いるアルカリ性の溶液としては、水酸化ナトリウム，水酸化カリウム等の水溶液が例として挙げられる。
The aluminum can is used as a container for various products, and since the surface is printed or painted, the present invention is reacted with an alkaline aqueous solution, and the remaining pigment is used with a solid-liquid separator. The feature is that the reaction solution can be reused.
Note that the printed layer or the coating layer on the surface may be removed by heating or dry distillation before or after crushing, and even in that case, the residue can be removed by a solid-liquid separator even if it cannot be completely removed.
This solid-liquid separator can also remove reaction residues such as aluminum hydroxide produced by the reaction between the alkaline aqueous solution and aluminum.
Examples of the alkaline solution used in the present invention include aqueous solutions of sodium hydroxide, potassium hydroxide and the like.
本発明において固液分離器は、傾斜面からなるフィルター部を有するようにするのが好ましい。
このようにすると、固形分はフィルターの傾斜面に沿って下部側に移動するので、この傾斜面の下部側に取出口を設けることで分離された固形分を系外に取り出すことが容易になる。
In the present invention, the solid-liquid separator preferably has a filter portion having an inclined surface.
If it does in this way, since solid content moves to the lower part side along the inclined surface of a filter, it will become easy to take out the separated solid content outside a system by providing an outlet in the lower part side of this inclined surface. .
本発明において、アルカリ性の反応液は水溶性の水素発生触媒を含有し、前記水素発生触媒はＦｅ２（ＳＯ４）３，ＦｅＣｌ３，Ｆｅ（ＮＨ４）（ＳＯ４）２，Ｎａ３ＰＯ４，（ＮＨ４）２Ｆ２（ＳＯ４）２，ＭｇＣｌ２，Ｃｏ（ＮＯ３）２，Ｋ２ＣＯ３，ＣｕＳＯ４，ＺｎＳＯ４，ＮａＦ，Ｎａ２ＳＯ４，ＮａＣｌＯ４のいずれかであるのが好ましい。
このように水溶液の触媒を用いると、固液分離器にて固形分と液体分を分離した場合に反応液側に残存し、繰り返し反応液として使用できる。
In the present invention, the alkaline reaction liquid contains a water-soluble hydrogen generating catalyst, and the hydrogen generating catalyst is Fe 2 (SO 4 ) 3 , FeCl 3 , Fe (NH 4 ) (SO 4 ) 2 , Na 3 PO 4. , (NH 4 ) 2 F 2 (SO 4 ) 2 , MgCl 2 , Co (NO 3 ) 2 , K 2 CO 3 , CuSO 4 , ZnSO 4 , NaF, Na 2 SO 4 , NaClO 4 Is preferred.
When an aqueous catalyst is used in this way, when the solid and liquid components are separated by a solid-liquid separator, they remain on the reaction solution side and can be used repeatedly as a reaction solution.
このような水素製造装置を用いたことにより、本発明に係る水素製造方法は、回収アルミ缶を破砕し、水溶性の水素発生触媒を含有するアルカリ性水溶液と反応させることで水素を発生させるステップと、前記反応終了後の反応終了液を斜めに傾斜させたフィルター部にて濾過するステップとを有し、
前記濾過された濾液を前記水溶性の水素発生触媒を含有するアルカリ水溶液として再利用することを特徴とする。
By using such a hydrogen production apparatus, the hydrogen production method according to the present invention includes a step of generating hydrogen by crushing a recovered aluminum can and reacting with an alkaline aqueous solution containing a water-soluble hydrogen generation catalyst. Filtering the reaction-terminated liquid after completion of the reaction through a slanted filter part,
The filtered filtrate is reused as an alkaline aqueous solution containing the water-soluble hydrogen generating catalyst.
本発明に係る水素製造に用いる原材料として回収アルミ缶を用いたので、安価に水素が製造でき、燃料電池に用いられる水素燃料として有用である。
さらには、水素ステーションに一体的に設けることもできる。
Since the recovered aluminum can is used as a raw material used for hydrogen production according to the present invention, hydrogen can be produced at low cost and is useful as a hydrogen fuel used in a fuel cell.
Furthermore, it can also be provided integrally with the hydrogen station.
以下、図に基づいて本発明に係る水素の製造装置及び製造方法例を説明する。
アルミとアルカリ水溶液とを反応させるための反応器１１と、この反応器１１に原材料を供給するホッパー部１３と、この反応器１１にアルカリ水溶液を供給するための反応液貯留タンク１２を有する。
図示を省略した破砕機にて回収したアルミ缶を小片状に破砕し、ホッパー部１３に投入する。
ホッパー部１３と反応器１１とは、フィーダー部１３ａにて接続され、原料となるアルミが連続的に反応器１１に投入可能になっている。
反応液貯留タンク１２には、アルカリ性の水溶液が貯留されており、反応器１１と配管接続され、バルブＶ１の開閉操作により、このアルカリ性の水溶液が反応器１１に供給制御される。
アルカリ性の水溶液は、水酸化ナトリウム，水酸化カリウム等の強アルカリ水溶液であり、前述の水溶性の水素発生触媒が溶解されている。
Hereinafter, a hydrogen production apparatus and a production method example according to the present invention will be described with reference to the drawings.
It has a reactor 11 for reacting aluminum and an aqueous alkali solution, a hopper 13 for supplying raw materials to the reactor 11, and a reaction liquid storage tank 12 for supplying an alkaline aqueous solution to the reactor 11.
The aluminum can collected by a crusher (not shown) is crushed into small pieces and put into the hopper 13.
The hopper unit 13 and the reactor 11 are connected by a
The reaction solution storage tank 12, and an alkaline aqueous solution is stored, the reactor 11 and connected by piping, by opening and closing operation of the valve V 1, an aqueous solution of the alkaline is controlled fed to the reactor 11.
The alkaline aqueous solution is a strong alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, in which the water-soluble hydrogen generating catalyst is dissolved.
反応器１１中では、アルミがアルカリ水溶液に溶解し、水素が発生する。
この水素は、バブルＶ４の開閉操作により、外部に取り出される。
反応が終了した水溶液は、バルブＶ２を開くことで、その下部に設けた固液分離器１４に流下する。
固液分離器１４には、溶液の冷却手段を備え、反応後の水溶液から水酸化アルミ等の固形分が析出する。
また、アルミ片に付着した顔料等の固形分も反応後の水溶液に含まれている。
これらの固形分は、斜めに配置したフィルター部１５の傾斜面に残留するが、傾斜面に沿って下部側に移動する。
これにより、フィルター部１５の下部側に設けた取出口１６から外部に排出しやすくなっている。
フィルター部１５の下側には、濾過液貯留部１７を設けてあり、濾液が貯留される。
水素発生触媒もこの濾液に溶解している。
そこで、バルブＶ３を開き、ポンプＰ１にて反応液貯留タンク１２に返送することで、反応液として繰り返し利用できる。
In the reactor 11, aluminum dissolves in the alkaline aqueous solution, and hydrogen is generated.
This hydrogen, by opening and closing operation of the bubble V 4, is taken out.
Solution the reaction is completed, by opening the valve V 2, and flows down to the solid-liquid separator 14 provided thereunder.
The solid-liquid separator 14 includes a solution cooling means, and a solid content such as aluminum hydroxide is precipitated from the aqueous solution after the reaction.
Moreover, solid content, such as a pigment adhering to the aluminum piece, is also contained in the aqueous solution after the reaction.
These solid contents remain on the inclined surface of the filter unit 15 disposed obliquely, but move to the lower side along the inclined surface.
Thereby, it becomes easy to discharge | emit outside from the extraction port 16 provided in the lower part side of the filter part 15. FIG.
A filtrate storage unit 17 is provided below the filter unit 15 to store the filtrate.
A hydrogen generating catalyst is also dissolved in the filtrate.
Therefore, by opening the valve V 3, by returning to the reaction solution storage tank 12 at pump P 1, repeat can be used as the reaction solution.
次に水素の製造方法について説明する。
ｐＨ＝１３以上の高濃度の水酸化ナトリウムの水溶液を反応液貯留タンクに準備し、この水溶液に０．００１〜０．１モル／リットルのＦｅ２（ＳＯ４）３を触媒として添加した。
これを反応器１１に供給し、アルミ缶を破砕した原料をホッパーから投入した。
実験装置では、１時間当たり２Ｋｇの水素を取り出すことができた。
反応液中には、コロイド状の副産物が生成されているとともに、顔料等の不純物も含まれていた。
これを固液分離器に流下させた。
濾過液中には、固定分がフィルター除去されており、反応液貯留タンク１２に戻した。
この返送した濾液は、再度反応液として使用できることも確認できた。
Next, a method for producing hydrogen will be described.
An aqueous solution of sodium hydroxide having a high concentration of pH = 13 or more was prepared in a reaction liquid storage tank, and 0.001 to 0.1 mol / liter of Fe 2 (SO 4 ) 3 was added to the aqueous solution as a catalyst.
This was supplied to the reactor 11, and the raw material obtained by crushing the aluminum can was introduced from the hopper.
In the experimental apparatus, 2 kg of hydrogen could be taken out per hour.
In the reaction solution, colloidal by-products were generated and impurities such as pigments were contained.
This was allowed to flow down to a solid-liquid separator.
In the filtrate, the fixed part was removed by filtration and returned to the reaction liquid storage tank 12.
It was also confirmed that the returned filtrate could be used again as a reaction solution.
１１ 反応器
１２ 反応液貯留タンク
１３ ホッパー部
１４ 固液分離器
１５ フィルター部
１６ 取出口
１７ 濾過液貯留部
DESCRIPTION OF SYMBOLS 11 Reactor 12 Reaction liquid storage tank 13 Hopper part 14 Solid-liquid separator 15 Filter part 16 Outlet 17 Filtrate storage part
Claims (4)
アルカリ性の反応液を貯留する反応液貯留タンクと、
前記破砕された回収アルミ缶と前記アルカリ性の反応液とを反応させる反応器を備え、
反応器で反応終了後の反応終了液を固液分離する固液分離器を有し、
前記固液分離器から得られた濾過液を前記反応液貯留タンクに返送する返送手段を有することを特徴とする水素製造装置。 A hopper section for feeding the crushed recovered aluminum can,
A reaction liquid storage tank for storing an alkaline reaction liquid;
A reactor for reacting the crushed recovered aluminum can and the alkaline reaction liquid;
It has a solid-liquid separator that separates the liquid after completion of reaction in the reactor into solid-liquid separation,
An apparatus for producing hydrogen, comprising return means for returning the filtrate obtained from the solid-liquid separator to the reaction liquid storage tank.
前記水素発生触媒はＦｅ２（ＳＯ４）３，ＦｅＣｌ３，Ｆｅ（ＮＨ４）（ＳＯ４）２，Ｎａ３ＰＯ４，（ＮＨ４）２Ｆ２（ＳＯ４）２，ＭｇＣｌ２，Ｃｏ（ＮＯ３）２，Ｋ２ＣＯ３，ＣｕＳＯ４，ＺｎＳＯ４，ＮａＦ，Ｎａ２ＳＯ４，ＮａＣｌＯ４のいずれかであることを特徴とする請求項１又は２記載の水素製造装置。 The alkaline reaction solution contains a water-soluble hydrogen generation catalyst,
The hydrogen generation catalyst is Fe 2 (SO 4 ) 3 , FeCl 3 , Fe (NH 4 ) (SO 4 ) 2 , Na 3 PO 4 , (NH 4 ) 2 F 2 (SO 4 ) 2 , MgCl 2 , Co ( 3. The hydrogen production apparatus according to claim 1, wherein the hydrogen production apparatus is any one of NO 3 ) 2 , K 2 CO 3 , CuSO 4 , ZnSO 4 , NaF, Na 2 SO 4 , and NaClO 4 .
前記反応終了後の反応終了液を斜めに傾斜させたフィルター部にて濾過するステップとを有し、
前記濾過された濾液を前記水溶性の水素発生触媒を含有するアルカリ水溶液として再利用することを特徴とする水素製造方法。 Crushing the recovered aluminum can and generating hydrogen by reacting with an alkaline aqueous solution containing a water-soluble hydrogen generating catalyst; and
Filtering the reaction-terminated liquid after completion of the reaction through a slanted filter part,
A method for producing hydrogen, wherein the filtered filtrate is reused as an alkaline aqueous solution containing the water-soluble hydrogen generating catalyst.
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| JP2021169391A (en) * | 2020-04-16 | 2021-10-28 | アルハイテック株式会社 | Method for producing hydrogen |
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| JP2021155239A (en) * | 2020-03-26 | 2021-10-07 | アルハイテック株式会社 | Method for recovering alkaline aqueous solution used for hydrogen production |
| JP7423055B2 (en) | 2020-03-26 | 2024-01-29 | アルハイテック株式会社 | Method for recovering alkaline aqueous solution used for hydrogen production |
| JP2021169391A (en) * | 2020-04-16 | 2021-10-28 | アルハイテック株式会社 | Method for producing hydrogen |
| JP2021169390A (en) * | 2020-04-16 | 2021-10-28 | アルハイテック株式会社 | Hydrogen generator |
| KR102206004B1 (en) * | 2020-07-21 | 2021-01-21 | 주식회사 패트리온 | Hydrogen fuel production system |
| JP7334974B2 (en) | 2020-10-05 | 2023-08-29 | アルハイテック株式会社 | Reaction liquid continuous supply type hydrogen generator |
| JP2022060707A (en) * | 2020-10-05 | 2022-04-15 | アルハイテック株式会社 | Reaction liquid continuous supply-type hydrogen generator |
| JP7495128B2 (en) | 2021-04-02 | 2024-06-04 | アルハイテック株式会社 | Hydrogen production method using aluminum alloy |
| KR20220158888A (en) * | 2021-05-24 | 2022-12-02 | 곽건화 | Hydrogen fuel production system having purifying function of hydrogen fuel |
| KR102581089B1 (en) | 2021-05-24 | 2023-09-22 | 곽건화 | Hydrogen fuel production system having purifying function of hydrogen fuel |
| CN113967449B (en) * | 2021-10-16 | 2022-08-12 | 江苏优普生物化学科技股份有限公司 | Chemical colloid production is with catalytic reaction equipment that has quantitative material loading structure |
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| CN114955993A (en) * | 2022-06-10 | 2022-08-30 | 天津大学 | Device for continuously producing hydrogen by photocatalytic degradation of polyester plastic |
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