JP6472098B2 - Hydrogen production method by recycling solid residue - Google Patents
Hydrogen production method by recycling solid residue Download PDFInfo
- Publication number
- JP6472098B2 JP6472098B2 JP2017118458A JP2017118458A JP6472098B2 JP 6472098 B2 JP6472098 B2 JP 6472098B2 JP 2017118458 A JP2017118458 A JP 2017118458A JP 2017118458 A JP2017118458 A JP 2017118458A JP 6472098 B2 JP6472098 B2 JP 6472098B2
- Authority
- JP
- Japan
- Prior art keywords
- solid residue
- hydrogen
- raw material
- mixed
- biomass resources
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Description
本発明は、バイオマス資源としてのセルロースや下水汚泥を水素製造の原料に用いた後の固体残渣の再利用による水素生成方法に関する。 The present invention relates to a method for generating hydrogen by reusing a solid residue after using cellulose or sewage sludge as a biomass resource as a raw material for hydrogen production.
従来から、バイオマスのエネルギー利用法の一つに熱分解やガス化のような熱化学的変換法がある。木質バイオマス試料の熱分解を行うと、ガスエンジンやメタノール合成等に利用できる熱分解ガスが出てくると同時に、副生成物として粘りのある油状液体のタールや、チャー（木炭）が出る。 Conventionally, there is a thermochemical conversion method such as pyrolysis and gasification as one of biomass energy utilization methods. When pyrolyzing woody biomass samples, pyrolysis gas that can be used for gas engines and methanol synthesis is produced, and at the same time, viscous oily liquid tar and char (charcoal) are produced as by-products.
チャーのガス化や燃焼を行う場合、全反応のうちで最も遅くなり全体の効率を低下させる要因となるので、バイオマスの熱化学的変換プロセスの中のチャーの生成挙動を調べることは重要なこととなってくる。また、チャーの収率や構造は、熱分解温度、昇温速度、圧力、無機物の含有成分等に依存することが知られている。 When char is gasified or burned, it is the slowest of all reactions and the overall efficiency is reduced, so it is important to investigate the char generation behavior in the biomass thermochemical conversion process. It becomes. In addition, it is known that the yield and structure of char depend on the thermal decomposition temperature, the temperature rise rate, the pressure, the inorganic components, and the like.
ところで、水素から燃料電池により電気及び熱を取り出すことは周知の技術であり、水素は重量当たりのエネルギー密度が高く、保管が可能なことからエネルギーキャリアとして有望である。また、純水素を燃料電池で使用する際に、大気汚染物質を排出しないことからクリーンな燃料であることが知られている。 By the way, it is a well-known technique to extract electricity and heat from hydrogen by a fuel cell, and hydrogen is promising as an energy carrier because it has a high energy density per weight and can be stored. In addition, when pure hydrogen is used in a fuel cell, it is known to be a clean fuel because it does not emit air pollutants.
バイオマスから水素ガスを製造する方法としては、特許文献１に開示されているように、バイオマス資源としてセルロースや下水汚泥に触媒として水酸化カルシウムと水酸化ニッケルを混合し、加熱することにより水素を生成させる構成（Ｃ＋２Ｈ２Ｏ→２Ｈ２＋ＣＯ２）とした特許技術が本出願人の先行技術となっている。 As disclosed in Patent Document 1, as a method for producing hydrogen gas from biomass, cellulose and sewage sludge as biomass resources are mixed with calcium hydroxide and nickel hydroxide as catalysts and heated to produce hydrogen. The prior art of the applicant of the present invention is a patented technology (C + 2H 2 O → 2H 2 + CO 2 ).
特許文献１では、加熱処理温度を約７００℃〜約８５０℃とした場合において、バイオマス資源と水酸化カルシウムと水酸化ニッケルの配合モル比率を１：（０．０１（ゼロではない）〜３．０）：（０．０１（ゼロではない）〜１．０）として混合し、且つ、解砕・混練し、この混合物を外熱炉へ供給して熱風と熱交換し昇温させ、更に、昇温時の加熱反応によって発生した各種生成ガスを減温除湿し、その一部を連続ガス分析計へ導入させるものとしている。 In Patent Document 1, when the heat treatment temperature is about 700 ° C. to about 850 ° C., the mixing molar ratio of biomass resources, calcium hydroxide and nickel hydroxide is 1: (0.01 (not zero) to 3. 0): (0.01 (not zero) to 1.0) are mixed, pulverized and kneaded, and the mixture is supplied to an external heating furnace to exchange heat with hot air to raise the temperature. Various product gases generated by the heating reaction at the time of temperature increase are dehumidified and dehumidified, and a part thereof is introduced into a continuous gas analyzer.
更に、特許文献２に開示されているように、バイオマスから水素ガスを製造する方法において、植物、植物から生産されたもの、古紙、家畜排せつ物、食品廃棄物、建築発生木材、又は、下水汚泥を含む廃棄物である高セルロース含有物の粉末と水酸化カルシウムの粉末と水酸化ニッケルの粉末とを所定量秤量し、該秤量物と複数の硬質ボールとを混合容器内に入れて所定時間混合粉砕して混合粉砕物とし、該混合粉砕物を密封容器内で３５０℃以上、４５０℃以下の温度に加熱保持し、発生した水素ガスを導出するという特許技術が本出願人の先行技術となっている。 Furthermore, as disclosed in Patent Document 2, in the method for producing hydrogen gas from biomass, plants, those produced from plants, waste paper, livestock excrement, food waste, building generated wood, or sewage sludge A predetermined amount of high cellulose-containing powder, calcium hydroxide powder, and nickel hydroxide powder, which are waste materials, are weighed, and the weighed material and a plurality of hard balls are placed in a mixing container and mixed and pulverized for a predetermined time. The prior art of the present applicant is a patented technique in which the mixed pulverized product is heated and held at a temperature of 350 ° C. or higher and 450 ° C. or lower in a sealed container to derive the generated hydrogen gas. Yes.
しかしながら、上記した特許文献１及び特許文献２においては、水素を作るために必要な触媒として水酸化ニッケルを使用しているが、ニッケル自体のコストが非常に高いものであり経済的とはいえなかった。 However, in Patent Document 1 and Patent Document 2 described above, nickel hydroxide is used as a catalyst necessary for producing hydrogen. However, the cost of nickel itself is very high, which is not economical. It was.
また、汚泥（固体残渣）の再利用を進めるとチャーが汚泥中に蓄積され、該チャー（木炭）の濃度が増加していく。上記した特許文献１及び特許文献２に係る水素製造技術を適用しようとする場合、安定的に所定の効果を得るためには汚泥（固体残渣）中に含まれる該チャーを削減する必要がある。 Further, when the sludge (solid residue) is reused, the char is accumulated in the sludge and the concentration of the char (charcoal) increases. When applying the hydrogen production technology according to Patent Document 1 and Patent Document 2 described above, it is necessary to reduce the char contained in the sludge (solid residue) in order to stably obtain a predetermined effect.
一方、該チャーは水素の原料ともなり得るため、これを原料とすれば該チャーの削減と水素生成量の増加が期待できることになる。因みに、汚泥（固体残渣）を観察すると、汚泥の中にはチャーの凝集体が形成されており、これを粉砕して微細化すれば該チャーの反応性が増加し、水素生成に大きく寄与することが考えられる。 On the other hand, since the char can also be a raw material for hydrogen, if this is used as a raw material, reduction of the char and an increase in the amount of hydrogen generation can be expected. Incidentally, when the sludge (solid residue) is observed, char aggregates are formed in the sludge, and if this is pulverized and refined, the reactivity of the char increases and greatly contributes to hydrogen generation. It is possible.
そこで、本発明は叙上のような従来存した諸事情に鑑み創出されたもので、水素を取り出したニッケル含有物を含む汚泥（固体残渣）を再利用して新しい汚泥と混ぜて循環させる汚泥循環型の水素生成リサイクルシステムを構築でき、これによりチャーの削減と水素生成量の増加との同時並行の効率化を容易に図ることができる固体残渣の再利用による水素生成方法を提供することを目的とするものである。 Therefore, the present invention was created in view of the existing circumstances as described above, and sludge containing nickel-containing material from which hydrogen is extracted (solid residue) is reused and mixed with new sludge to circulate. To provide a hydrogen generation method by reusing solid residue, which can build a recycling type hydrogen generation and recycling system, and can easily improve the efficiency of simultaneous reduction of char and increase of hydrogen generation. It is the purpose.
上述した課題を解決するために、本発明にあっては、バイオマス資源としてのセルロースや下水汚泥に水酸化カルシウム及び水酸化ニッケルを混合し、加熱することにより水素を生成する水素生成方法において、前記バイオマス資源に水酸化カルシウム及び水酸化ニッケルを混合した新規原料に、水素ガスを製造した後のニッケル含有物を含む固体残渣を追加混入して加熱処理してなることを特徴とする。 In order to solve the problems described above, in the present invention, in the hydrogen generation method for generating hydrogen by mixing calcium hydroxide and nickel hydroxide with cellulose and sewage sludge as biomass resources and heating, A new raw material in which calcium hydroxide and nickel hydroxide are mixed with biomass resources is additionally mixed with a solid residue containing a nickel-containing material after producing hydrogen gas, and is heat-treated.
また、上記固体残渣は、バイオマス資源から水素ガスを製造した後のチャーが残留している再利用可能なもので、粉砕工程により粉砕して微細化され、微細化された固体残渣を不活性ガスを含む水蒸気雰囲気で熱分解する加熱工程により加熱処理されてなることを特徴とする。 The solid residue is a reusable one in which char remains after hydrogen gas is produced from biomass resources. The solid residue is pulverized and refined by a pulverization process, and the refined solid residue is converted into an inert gas. It is heat-processed by the heating process thermally decomposed in the water vapor atmosphere containing this.
更に、上記粉砕工程により、固体残渣中の固定炭素を含むチャーを１０ミクロン以下に微細化することにより水素の生成量を増加させることを特徴とする。 Furthermore, the amount of hydrogen generation is increased by reducing the char containing fixed carbon in the solid residue to 10 microns or less by the pulverization step.
また、上記加熱工程は、加熱処理温度を約７００℃〜約８５０℃とし、バイオマス資源と水酸化カルシウム及び水酸化ニッケルの混合割合を１：（０．０１（ゼロでない）〜３．０）：（０．０１（ゼロを含む）〜３．０）とし、新規原料と固体残渣の割合を１：（０．０１（ゼロでない）〜２０．０）としてなることを特徴とする。 In the heating step, the heat treatment temperature is about 700 ° C. to about 850 ° C., and the mixing ratio of biomass resources, calcium hydroxide and nickel hydroxide is 1: (0.01 (not zero) to 3.0): (0.01 (including zero) to 3.0), and the ratio of the new raw material to the solid residue is 1: (0.01 (not zero) to 20.0).
更に、上記加熱工程は、前記粉砕工程で微細化された固体残渣を原料として、固体残渣仕込み量として約２ｇを、加熱手段によって熱分解温度約５５０℃〜約６５０℃、昇温速度約５０℃／ｍｉｎ、加熱時間約１時間、水滴下量約０．０５ｍＬ／１０ｓ、不活性ガス流量約５ｍＬ／ｍｉｎという条件にて加熱分解処理することで水素を生成することを特徴とする。 Further, in the heating step, the solid residue refined in the pulverization step is used as a raw material, and about 2 g is charged as a solid residue. / Min, heating time of about 1 hour, water dropping amount of about 0.05 mL / 10 s, and inert gas flow rate of about 5 mL / min.
本発明によれば、水素を取り出した後のニッケル含有物を含む汚泥（固体残渣）を再利用して新しい汚泥と混ぜて循環させる汚泥循環型の水素生成リサイクルシステムを構築でき、チャーの削減と水素生成量の増加とを同時並行により行うことで効率化を図ることが可能となった。 According to the present invention, it is possible to construct a sludge circulation type hydrogen generation and recycling system that recycles sludge (solid residue) containing nickel-containing material after taking out hydrogen and mixes and circulates it with new sludge. It has become possible to improve efficiency by simultaneously increasing the amount of hydrogen produced.
以下、図面を参照して本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
本実施形態においては、バイオマス資源としてのセルロースや下水汚泥に水酸化カルシウム及び水酸化ニッケルを混合した新規原料に、水素ガスを製造した後のニッケル含有物を含む固体残渣を追加混入して加熱処理する固体残渣循環型の水素生成システムとしている。 In the present embodiment, heat treatment is performed by additionally mixing a solid residue containing nickel-containing material after producing hydrogen gas into a new raw material in which calcium hydroxide and nickel hydroxide are mixed with cellulose and sewage sludge as biomass resources. This is a solid residue circulation type hydrogen generation system.
また、本実施形態では、水素を取り出したニッケル含有物を含む汚泥（固体残渣）を再利用して新しい汚泥と混ぜて循環する方式を採っている仕組みの中で、水素を取り出したチャーを含む汚泥（固体残渣）に対して粉砕処理による操作を加えることで水素の生成量が増えることをバッチ試験で確認した。このことは、固体残渣中にチャーの凝集体が形成され、これを粉砕して微細化すればチャーの反応性が増し、水素生成に寄与するものと考えられるからである。 Moreover, in this embodiment, the char which extracted hydrogen is included in the system which has taken the system which reuses sludge (solid residue) containing nickel content which extracted hydrogen, mixes with new sludge, and circulates. It was confirmed by a batch test that the amount of hydrogen produced increased by adding an operation by pulverization to sludge (solid residue). This is because an aggregate of char is formed in the solid residue, and if this is pulverized and refined, it is considered that the reactivity of char increases and contributes to hydrogen generation.
すなわち、本実施形態における固体残渣循環型の水素生成システムでは、図１に示すように、バイオマスから水素ガスを製造した後のチャーが残留している再利用可能な固体残渣を粉砕し微細化する粉砕工程Ａと、微細化された固体残渣を不活性ガスを含む水蒸気雰囲気で熱分解する加熱工程Ｂと、を有する。 That is, in the solid residue circulation type hydrogen generation system according to the present embodiment, as shown in FIG. 1, the reusable solid residue in which char remains after hydrogen gas is produced from biomass is pulverized and refined. A pulverization step A, and a heating step B in which the refined solid residue is thermally decomposed in a water vapor atmosphere containing an inert gas.
粉砕工程Ａは、例えば、固体残渣の２ｇ当たりを遊星ミル（例えば、ボールミル等）に投入し、回転数７００ｒｐｍで約３０分間粉砕することで、固体残渣中の固定炭素を含むチャーを１０ミクロン以下に微細化する。 In the pulverization step A, for example, 2 g of the solid residue is charged into a planetary mill (for example, a ball mill) and pulverized at a rotation speed of 700 rpm for about 30 minutes, so that the char containing the fixed carbon in the solid residue is 10 microns or less. To make it finer.
加熱工程Ｂは、加熱処理温度を約７００℃〜約８５０℃とし、バイオマス資源と水酸化カルシウム及び水酸化ニッケルの混合割合を１：（０．０１（ゼロでない）〜３．０）：（０．０１（ゼロを含む）〜３．０）とし、新規原料と固体残渣の割合を１：（０．０１（ゼロでない）〜２０．０）とする。 In the heating step B, the heat treatment temperature is about 700 ° C. to about 850 ° C., and the mixing ratio of biomass resources, calcium hydroxide and nickel hydroxide is 1: (0.01 (not zero) to 3.0) :( 0 0.01 (including zero) to 3.0), and the ratio of the new raw material to the solid residue is 1: (0.01 (not zero) to 20.0).
更に、具体的には、加熱工程Ｂは、前記粉砕工程Ａで微細化された固体残渣を原料として、図２に示す電気炉３等の加熱手段によって、固体残渣仕込み量として約２ｇを、熱分解温度約５５０℃〜約６５０℃で好ましくは約６００℃、昇温速度約５０℃／ｍｉｎ、加熱時間約１時間、水滴下量約０．０５ｍＬ／１０ｓ、不活性ガス流量約５ｍＬ／ｍｉｎという条件にて加熱分解処理することで水素を生成する。 More specifically, in the heating step B, the solid residue refined in the pulverization step A is used as a raw material, and about 2 g of solid residue is charged by a heating means such as the electric furnace 3 shown in FIG. The decomposition temperature is about 550 ° C. to about 650 ° C., preferably about 600 ° C., the heating rate is about 50 ° C./min, the heating time is about 1 hour, the water dripping amount is about 0.05 mL / 10 s, and the inert gas flow rate is about 5 mL / min. Hydrogen is produced by thermal decomposition treatment under conditions.
次に、加熱工程Ｂで使用されるバッチ試験用の回分式水素直接製造装置の構成について、図２に基づき説明する。 Next, the configuration of the batch type hydrogen direct production apparatus for batch test used in the heating step B will be described with reference to FIG.
回分式水素直接製造装置は、図２に示すように、固体残渣である試料Ｐが試験管１内に投入され、試験管１は縦長の円筒型空洞状に形成された密閉された石英管２内に収容されている。石英管２は筒状の電気炉３の内部にセットされる。 As shown in FIG. 2, in the batch type hydrogen direct production apparatus, a sample P, which is a solid residue, is put into a test tube 1, and the test tube 1 is a sealed quartz tube 2 formed in a vertically long cylindrical cavity. Is housed inside. The quartz tube 2 is set inside a cylindrical electric furnace 3.
石英管２の上端側は、水量調節装置４Ａを介して蒸留水タンク４に接続され、試験管１内に蒸留水を投入する。また、石英管２の上端側は、流量計５Ａ及びバルブ５Ｂを介して、不活性ガス（例えばアルゴンガス：Ａｒ）タンク５に接続されている。 The upper end side of the quartz tube 2 is connected to the distilled water tank 4 via the water amount adjusting device 4A, and distilled water is poured into the test tube 1. The upper end side of the quartz tube 2 is connected to an inert gas (eg, argon gas: Ar) tank 5 via a flow meter 5A and a valve 5B.
更に、石英管２の上端側の側壁面には、試料Ｐから生成された水素ガスを導出するための導管６Ａが下方に向けて延設され、導管６Ａの先端開口側は冷却トラップ装置６内の捕集容器６Ｂ内に挿入されている。 Further, on the side wall surface on the upper end side of the quartz tube 2, a conduit 6 </ b> A for deriving hydrogen gas generated from the sample P is extended downward, and the tip opening side of the conduit 6 </ b> A is inside the cooling trap device 6. Is inserted into the collection container 6B.
また、冷却トラップ装置６内にはここで冷却された水素ガスを排出するための排気管７Ａの一端開口部が挿入され、該排気管７Ａの他端開口部は、流路選択装置７を介して、アスピレータ８及び二重水槽による捕集用シリンダ９に分岐して接続されている。 One end opening of an exhaust pipe 7A for discharging the hydrogen gas cooled here is inserted into the cold trap device 6, and the other end opening of the exhaust pipe 7A passes through the flow path selection device 7. Then, it is branched and connected to a collecting cylinder 9 by an aspirator 8 and a double water tank.
次に、パイロットプラント試験の概要について説明すると、図３に示すように、第１回の試験では、第２回の試験に供するための固体残渣を製造することと、加熱温度の影響を明確にすることを目的として、固体残渣の再利用率０％で熱風温度を６７０℃と８４０℃として水素の生成を行った。 Next, the outline of the pilot plant test will be described. As shown in FIG. 3, in the first test, the solid residue for use in the second test is manufactured and the influence of the heating temperature is clarified. For this purpose, hydrogen was generated at a hot air temperature of 670 ° C. and 840 ° C. with a solid residue reuse rate of 0%.
図３に示すように、第２回（試験番号２−１、２−２）では、固体残渣の再利用率を０％及び１０％、第３回（試験番号３−１、３−２）では、３０％及び５０％、第４回（試験番号４−１、４−２）では、７０％及び９０％とした。なお、第４回（試験番号４−１、４−２）の試験においては、脱水汚泥の水分量が高く、水分の蒸発に熱が使われるため、試料の投入量を減少させた。脱水汚泥の水分量が高いと投入トラブルや熱の損失に繋がるため、事業性評価においては、脱水汚泥を予備乾燥することとした。 As shown in FIG. 3, in the second round (test numbers 2-1 and 2-2), the solid residue reuse rates were 0% and 10%, and the third round (test numbers 3-1 and 3-2). Then, 30% and 50%, and in the fourth round (test numbers 4-1 and 4-2), they were 70% and 90%. In the fourth test (Test Nos. 4-1 and 4-2), the amount of dehydrated sludge was high and heat was used to evaporate the water, so the amount of sample input was reduced. If the water content of dewatered sludge is high, it will lead to input trouble and heat loss. Therefore, it was decided to predry dehydrated sludge in the business evaluation.
次に、固体残渣を粉砕することが水素生成に及ぼす影響について説明する。先ず、試験番号３−１の固体残渣のみを遊星ミルを用いて約７００ｒｐｍで約３０分間粉砕し、これを原料として、上記した回分式水素直接製造装置を用いて水素生成のバッチ実験を行った。その結果、固体残渣１ｋｇ当たり３．８ｇの水素が生成されることが判明した。 Next, the effect of pulverizing the solid residue on hydrogen generation will be described. First, only the solid residue of test number 3-1 was pulverized at about 700 rpm for about 30 minutes using a planetary mill, and using this as a raw material, a batch experiment for hydrogen generation was performed using the batch hydrogen direct production apparatus described above. . As a result, it was found that 3.8 g of hydrogen was produced per 1 kg of the solid residue.
一方、粉砕を行わなかった場合は、固体残渣１ｋｇ当たり０．８ｇの水素が生成されるので、水素の増加分は３．０ｇ／ｋｇ（固体残渣）となった、 On the other hand, when pulverization was not performed, 0.8 g of hydrogen was produced per 1 kg of the solid residue, so the increase in hydrogen was 3.0 g / kg (solid residue).
これを試験番号４−２に適用し、１．３ｋｇ／ｈの固体残渣をパイロットプラントに装入したとすると、０．７３Ｌ／ｍｉｎの水素の増加が見込まれ、水素生成量は２．９５Ｌ／ｍｉｎが、３．６８Ｌ／ｍｉｎになり、約２５％の水素の生成増加に繋がる。 If this is applied to test number 4-2 and 1.3 kg / h of solid residue is charged into the pilot plant, an increase of 0.73 L / min of hydrogen is expected, and the hydrogen production amount is 2.95 L / min. Min becomes 3.68 L / min, which leads to an increase in hydrogen production of about 25%.
パイロットプラントによる水素生成量の結果として、例えば、図４に示すように、試験番号３−１、３−２の試験時には、汚泥中の水分量が多いことから、サンプルがアジテータに付着し、更に、この水分により水酸化ニッケルが水分を含み本装置の混練機壁に付着してしまい、サンプル送りが均一でなかったためと、ガス測定装置の不調が重なり、水素の生成が極端に少なくなっている。試験番号２−２は、水素濃度の上昇中に分析用のガス採取を行った。 As a result of the amount of hydrogen produced by the pilot plant, for example, as shown in FIG. 4, during the tests of test numbers 3-1, 3-2, the amount of water in the sludge is large, so that the sample adheres to the agitator, Because of this moisture, the nickel hydroxide contains moisture and adheres to the kneader wall of this device, and the sample feeding is not uniform, and the gas measuring device malfunctions, resulting in extremely low hydrogen production. . In test number 2-2, gas for analysis was collected while the hydrogen concentration was increasing.
試験番号４−２の固体残渣再利用率約９０％において、単位量当たりの水素の生成量が固体残渣再利用率０％と略同じであり、固体残渣を再利用しても水素生成量は大きく減少しないことが解る。 When the solid residue reuse rate of test number 4-2 is about 90%, the amount of hydrogen generated per unit amount is substantially the same as the solid residue reuse rate of 0%. It turns out that it does not decrease greatly.
パイロットプラントによる固体残渣の有機微量分析の結果として、図５に示すように、固体残渣中の炭素（Ｃ）濃度が、１１．７８〜１５．４７と、試験回数（試験番号２−１〜４−２）が増えると増加している。これは、下水汚泥が炭化され、チャーとして残留し、それが回数を重ねる度に蓄積されていくためであると考えられる。 As a result of the organic microanalysis of the solid residue by the pilot plant, as shown in FIG. 5, the carbon (C) concentration in the solid residue was 11.78 to 15.47, and the number of tests (test numbers 2-1 to 4). -2) increases as it increases. This is thought to be because sewage sludge is carbonized and remains as char and accumulates every time it is repeated.
図６に示すように、上記した回分式水素直接製造装置の固体残渣と、パイロットプラント試験（試験番号３−１）の固体残渣の形態を観察するためのＳＥＭ（走査電子顕微鏡）観察とマッピングを行った。その結果、回分式水素直接製造装置においては、ニッケルは数μｍの粒子が分散しているのに対し、パイロットプラント試験では、数十μｍの粒子となって存在している。 As shown in FIG. 6, SEM (scanning electron microscope) observation and mapping for observing the form of the solid residue of the batch hydrogen direct production apparatus described above and the solid residue of the pilot plant test (Test No. 3-1) went. As a result, in the batch type hydrogen direct production apparatus, nickel has a particle size of several μm, whereas in a pilot plant test, it exists as a particle of several tens μm.
以上、説明したように、本実施形態においては、水素を取り出したニッケル含有物を含む汚泥（固体残渣）を再利用して新しい汚泥と混ぜて循環させる汚泥循環型の水素生成リサイクルシステムを構築でき、チャーの削減と水素生成量の増加との同時並行の効率化を容易に図ることが可能となった。 As described above, in this embodiment, it is possible to construct a sludge circulation type hydrogen generation and recycling system that recycles sludge (solid residue) containing nickel extracted from hydrogen and mixes it with new sludge and circulates it. Thus, it has become possible to easily improve the efficiency simultaneously with the reduction of char and the increase of hydrogen production.
Ａ 粉砕工程
Ｂ 加熱工程
Ｐ 試料（固体残渣）
１ 試験管
２ 石英管
３ 電気炉
４ 蒸留水タンク
４Ａ 水量調節装置
５ 不活性ガスタンク
５Ａ 流量計
５Ｂ バルブ
６ 冷却トラップ装置
６Ａ 導管
６Ｂ 捕集容器
７ 流路選択装置
７Ａ 排気管
８ アスピレータ
９ 捕集用シリンダ
A grinding process B heating process P sample (solid residue)
DESCRIPTION OF SYMBOLS 1 Test tube 2 Quartz tube 3 Electric furnace 4 Distilled water tank 4A Water quantity adjustment device 5 Inert gas tank 5A Flow meter 5B Valve 6 Cooling trap device 6A Conduit 6B Collection container 7 Flow path selection device 7A Exhaust pipe 8 Aspirator 9 For collection Cylinder
Claims (7)
Heating step, a finely divided solid residue as powdery砕工as a raw material, a 2 g as a solid residue渣仕penetration depth of thermal decomposition temperature of 5 50 ℃ ~6 50 ℃ by the heating means, NoboriAtsushisoku degree 5 0 ° C. / min, 1 hour between the time of heating, water dripping amount 0. 05mL / 10s, generating hydrogen by re-use of any description of the solid residue of claims 3 to 5, characterized in that to produce hydrogen by thermal decomposition treatment under conditions that the inert gas flow amount 5 mL / min Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017118458A JP6472098B2 (en) | 2017-06-16 | 2017-06-16 | Hydrogen production method by recycling solid residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017118458A JP6472098B2 (en) | 2017-06-16 | 2017-06-16 | Hydrogen production method by recycling solid residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019001928A JP2019001928A (en) | 2019-01-10 |
| JP6472098B2 true JP6472098B2 (en) | 2019-02-20 |
Family
ID=65005816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017118458A Active JP6472098B2 (en) | 2017-06-16 | 2017-06-16 | Hydrogen production method by recycling solid residue |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6472098B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112355034A (en) * | 2020-11-17 | 2021-02-12 | 同济大学 | Organic solid waste harmless pretreatment method based on hydrothermal calcium ion blending |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023190447A1 (en) * | 2022-03-30 | 2023-10-05 | 国立大学法人東北大学 | Transition metal nanoparticle carrier and method for producing transition metal nanoparticle carrier |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH093461A (en) * | 1995-06-16 | 1997-01-07 | Mitsubishi Heavy Ind Ltd | Circulating feeder for unreacted char |
| JP2003342588A (en) * | 2002-05-27 | 2003-12-03 | Setec:Kk | Biomass gasification equipment |
| JP2004115688A (en) * | 2002-09-27 | 2004-04-15 | Jfe Plant & Service Corp | Method and apparatus for gasifying waste |
| WO2010008082A1 (en) * | 2008-07-18 | 2010-01-21 | Hatta Akimichi | Process for production of useful gas |
| JP6570111B2 (en) * | 2015-05-28 | 2019-09-04 | 国立大学法人東北大学 | Hydrogen production method and system |
-
2017
- 2017-06-16 JP JP2017118458A patent/JP6472098B2/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112355034A (en) * | 2020-11-17 | 2021-02-12 | 同济大学 | Organic solid waste harmless pretreatment method based on hydrothermal calcium ion blending |
| US11344934B2 (en) | 2020-11-17 | 2022-05-31 | Tongji University | Method for harmlessly pretreating organic solid waste based on combination of calcium ion and hydrothermal treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019001928A (en) | 2019-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Co-pyrolysis of waste tire and pine bark for syngas and char production | |
| Wang et al. | Hydrogen-rich syngas production from biomass pyrolysis and catalytic reforming using biochar-based catalysts | |
| Ma et al. | Gasification of rice husk in a downdraft gasifier: the effect of equivalence ratio on the gasification performance, properties, and utilization analysis of byproducts of char and tar | |
| Van Huynh et al. | Performance characteristics of a pilot-scale biomass gasifier using oxygen-enriched air and steam | |
| Nejati et al. | Catalytic pyrolysis and bio-products upgrading derived from Chlorella vulgaris over its biochar and activated biochar-supported Fe catalysts | |
| Zeng et al. | Solar pyrolysis of heavy metal contaminated biomass for gas fuel production | |
| Gai et al. | Pyrolysis behavior and kinetic study of phenol as tar model compound in micro fluidized bed reactor | |
| Liu et al. | Comparison between hydrogen-rich biogas production from conventional pyrolysis and microwave pyrolysis of sewage sludge: is microwave pyrolysis always better in the whole temperature range? | |
| Tursunov et al. | Studies of CO 2 gasification of the Miscanthus giganteus biomass over Ni/Al 2 O 3-SiO 2 and Ni/Al 2 O 3-SiO 2 with K 2 O promoter as catalysts | |
| JP6472098B2 (en) | Hydrogen production method by recycling solid residue | |
| Zhang et al. | Tailoring of structural and optical parameters of corncobs through ball milling pretreatment | |
| Zhang et al. | Effect of washing pretreatment with aqueous fraction of bio-oil on pyrolysis characteristic of rice husk and preparation of amorphous silica | |
| ZHAO et al. | Transformation of alkali and alkaline earth metallic species during pyrolysis and CO2 gasification of rice straw char | |
| Yang et al. | Thermochemical conversion of lignocellulosic bio-waste via fast pyrolysis in molten salts | |
| Hossain et al. | Catalytic microwave pyrolysis of oil palm fiber (OPF) for the biochar production | |
| Li et al. | Ash fusion behaviors of sugarcane bagasse and its modification with sewage sludge addition | |
| JP5117253B2 (en) | Nanocarbon production equipment | |
| WO2021072684A1 (en) | Method for preparing biochar and hydrogen by utilizing anaerobic fermentation byproduct | |
| Lin et al. | Valorization of sludge using microwave pyrolysis for green bio-energy: combined effects of key parameters on the directional optimization of high-quality syngas | |
| Attasophonwattana et al. | Evolving circular economy in a palm oil factory: Integration of pilot-scale hydrothermal carbonization, gasification, and anaerobic digestion for valorization of empty fruit bunch | |
| Du et al. | Pyrolysis of rubber seed oil over high-temperature copper slag: Gas and mechanism of coke formation | |
| Li et al. | Enhancement of coke gasification by lignite and a low-cost Fe/red mud catalyst to produce syngas | |
| EP3031880A1 (en) | Dry distillation reactor and method for raw material of hydrocarbon with solid heat carrier | |
| Gujar et al. | Oxygen-blown gasification of pine charcoal in a top-lit downdraft moving-hearth gasifier | |
| Jiang et al. | Design and operation of a fixed-bed pyrolysis-gasification-combustion pilot plant for rural solid waste disposal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190117 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190118 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6472098 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |