2011水素発表資料.ppt
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1 .0.3 水素エネルギシステム 水電気分解 H O = H + O ΔH 水素製造 熱分解 ISプロセス 水蒸気改質 CH4+HO=CO+3H 原子力- 高温水素製造に関する 話題 部分酸化 CH4+O=CO+4H 水素輸送 水素貯蔵 液体水素 水素ガス 九州大学総合理工学研究院 深田智 M+ GTL, DME メタノールH+CO=CH3OH ベンゼン(シクロヘキサン) 水素利用 ナフタリン(デカリン) n H = MHn 金属水素化物 カーボン 溶融塩(NaAlH4, NaBH4) 燃料電池 H + O = O + ΔH 自動車や航空機 水素タービン 工業的 K++HO+e-=KOH+H OH-=HO+/O+e- G値 (KOH水溶液) C+HO=CO+H (NaCl電気分解) (G値として整理) Carbon dioxide Capture and Storage 3 4
2 CH 4 mole +00kJ CH 4 + = O+C CH 4 + O=4 +C He 0Wh 50% 40kJ 50% 06Wh Q Brayton cycle η= γ γ p H = p = p 3 = T γ T γ = 3 p L p p 4 T T 4 T T 4 γ η = T = T = p γ L = p 0.4 L, He T T 3 T T p H p H, He T -Q 4 p H γ = c P c V c P c V = R g p H p L p L
3 .0.3 On overall thermal efficiency of HTGR Heat- to- electricity HO H + /O ηmax=- TL/ TH Carnot cycle 50% 酸化法 : A=Fe, Mg, SO A+HO=AO+H AO=A+/O 還元法 : B=Cl, Br, I B+HO=BH+/O BH=B+H PEM electrolysis u@liza@on Thermo- chemical water splidng Heat- to- H 90% HTGR 45% 水から水素を製造 Genera@on of electricity by gas turbine H- to- electricity 9 0 熱化学法による代表的水素製造法 3
4 of Nuclear of by I- S cycle AYer the Bunsen exothermic reac@on S + I + O HI + SO 4 ΔH 4 Three different temperatures according to endothermic reac@on SO 4 (aq) O(g) + SO 3 (g) + ΔH C SO 3 (g) S (g) (g) + Δ C HI + I + ΔH o C O = ΔH 0 ΔH 0 = ΔH + Δ + ΔH 3 ΔH 4 4 Chemical heat pump to enhance heat u@liza@on of HTGR utilization of heat T in T L =T L gas turbines T H T L HTGR T =T H (He gas coolant) HI +I 300 o C T M3 SO 4 O+SO o C T M T M T H T M B+b/ BH b +ΔH AH b +ΔH A+b/ T M3 T M chemical heat pump SO 3 S o C T M Bunsen reaction O+S +I HI+ SO 4 5 Fig. 5 Chemical heat-pump system matched to temperature of I-S cycle and HTGR
5 y-intercept ΔS Thermodynamic of hydride: M + (n/) = MH n + ΔH Equilibrium pressure Equilibrium pressure p A,M t 3 t t T M T M T H T M T M Alloy A Alloy B p H t t 4 t 3 T M3 T L Alloy A Zr ΔH= - 63kJ/mol- LiH ΔH= - 57kJ/mol- La ΔH= - 00kJ/mol- ZrV H 4.8 ΔH= - 00kJ/mol- p B,M p M3 t t 6 t 5 t 5 t 6 p L ΔS= kj/mol- K independent of alloys or metals t 4 Fig. 3 Van t Hoff plot for hydrogen- absorbing alloys AH a or BH a AH b or BH b Hydrogen-to-alloy atomic ratio H/M Equilibrium pressure of Zr(V - X Fe X ) alloys ZrV H 4.8 ΔH= - 00kJ/mol- p H =0-8 atm ZrFe ΔH=0 p H =00atm ZrV + ZrFe also composes C5- Laves phase hydride. Fig. 6 Heat pump cycle on van t Hoff plot Log(p) p A,M P B,H p B,M p A,L Heat extract Mb+ Mb Mb Mb+ Heat supply Heat supply Ma Ma+ Two alloy beds Zr(V - X Fe X ) are placed in parallel. Alloy B T M Heat T H Ma Ma+ Heat extract Ma+ MaH X Alloy A Mb+ Mb Fig. 4 ΔH or p H depend on composi@on of C5- Laves phase of Zr(V - X Fe X ) 900 o C 300 o C- 500 o C /T H /T M /T L SO 3 S + Reactor heat SO 4 O+SO 3 HI +I /T
6 Experiment of heat in ZrV.9 Fe 0. alloys Synthesize ZrV.9 Fe 0. alloy from Zr, V and Fe Set up absorp@on/desorp@on apparatus Ac@vate ZrV.9 Fe 0. alloy par@cles Introduce under constant flow rate Measure temperature in ZrV.9 Fe 0. alloy bed Temperature eleva@on of ZrV.9 Fe 0. alloy par@cle bed Time (absorp@on) Desorb ZrV.9 Fe 0. par@cle bed Heat up to T 0 Cut off electricity of furnace (stop hea@ng) Supply under constant flow rate Measure T inside ZrV.9 Fe 0. par@cle bed Whether or not the alloy can absorb and desorb at I- S cycle? q 0 :maximum amount of hydrogen absorbed Fig. 7 Experimental apparatus for basic study of Ze- V- Fe alloys heat pump Fig. 8 Temperature eleva@on vs. absorbed amount Temperature eleva@on during absorp@on When W<3.5L/min, ΔT depends on W. When W>3.5L/min, ΔT is independent of W. Desorp@on from ZrV.9 Fe 0. alloy bed by hea@ng ZrV.9 Fe 0. can desorb only by pressure difference between two beds with any external force. This is because ΔH due to hydrogena@ng is consumed for gas hea@ng. Heat supply rate is constant. Fig. 9 Temperature eleva@on vs. temperature of introduced Fig. 0 He desorp@on rate and temperature as a func@on
7 .0.3 High- temperature H u@liza@on system comprised of HTGR, H produc@on plant, heat pump, H storage bed, ceramic fuel cell 水素によるクリーンエネルギーシステム 太田時男 サイエンス Vol.3(5) (974) p Fig. High-temperature H utilization system 5 6 H permeable membrane tube supplied with CH4 Methods to produce H from CH4 Water- reforming CH4 + HO = CO + 3H Par@al oxida@on CH4 + O = CO + H Reac@on mechanism 燃料排ガス中のメタン分解回収のためのニッケル 製透過反応器の性能評価 Prettre(946) Complete oxidation 3CH4 CH4 + O CO + HO 4(CO + H ) Need catalyst, need to supply heat, 800oC Overall reaction (Texaco method) No catalyst, no need to supply heat 300oC Two-step reaction of CH4 reforming Hickman(993) (/)O CH4 C + 4H* CO + H Separation Science and Technology, 37 (00) Direct catalytic oxidation of CH4 use catalyst, 700oC Journal of Nuclear Science and Technology, 38 (00) 73-77, 4(005) 305-3, Catalyst bed Journal of Nuclear Materials, 333 (004) , 348 (006) 8-3. CH4+O J. Radio-analytical and Nuclear Chemistry, 6 (004) H, CO, HO, CO, CH4, O International Journal of Hydrogen Energy, 9 (004) 69-65, Fusion Science and Technology, (006) 7 8 7
8 O Support material mechanism proposed H CH 4 C Ni particle (Prettre & Hickman) C C CH 4 CO O C H CO Ni particle O Reactant product (Prettre) O Support material 9 ΔG values of CH 4 oxida@on CH 4 + = CO + CH 4 + C = CO + CH 4 + O = CO + 3 CH 4 + = C + O CO + O = C + CO + = C + = O Material balance of C, H, O in up CH4 in 4up CH 4 up in O in p CH4 p CH4 () () (3) (4) (5) (6) (7) = v p ( CO + p C + p CH4 ) ΔG i [kj/mol] 00 (3) (8) 0 (5) () (7) (6) (4) ()CH 4 +(/) =CO+ ()CH 4 +C =CO+ (3)CH 4 + O=CO+3 (4)CH 4 + =C + O (5)CO+ O=C + (6)CO+(/) =C (7) +(/) = O 400 vx H () (8)CH 4 =C+ 800 Fig. 3 conversion ratio Temperature [K] H η = mole in = v p + p in = ux product ( O + 4p CH4 ) CH 4 CH 4 mole in feed = v p CO + p CO +p + p Catalyst bed ( O ) H O u v CH 4 +, CO, O, + p in O = p in C, CH 4, p = p in + ΔP + p O + p + p H O + p CO + p CO = p Effects of temperature and on let concentra@on Hydrogen permeability through Ni and comparison with Pd (i=, C, CO, CH 4,, O) x i in in - x exp. cal. CH4 =0.67, xo =0.33, W=0.6sec CO CH 4 CH 4 C O O C CO 0.4 in in 873K, x CH4 =0.67, xo =0.33 CH 4 - to- conversion was almost independent of T < 900K : CH 4 O and C Conversion is very fast T > 900K : CH 4 and CO (i=,co,ch 4,,C, O) x i Superficial gas velocity [sec - ] CO CH 4 C O Fig. 4 Temperature [K] Fig. 5 Contact time [s] CH 4-3
![Ni/Si CH 4 CH 4 Ni/Si CH 4 Overall decomposition rate constant, k decomp [sec - ] 0 6 5 4 3 6 5 4 3 0. 0.9 800 700 600 500 [C] k decomp =3.09x0 exp(-9.5[kj/mol]/r g T).0. 000/T [K - ] -CH 4 system Ar-CH 4 system.](/docs-images/92/109822011/images/9-2.jpg ".3 CH 4 C+ CH 4 + * CH 3 * + H* CH 3 * + * = C * + H* C * + * = CH* + H* CH* = C + H* H* = + * k decomp :(/s) k decomp = k F a V k F : x CH4, /x CH4,in x CH4 33 p CH 4, p CH 4,s p CH 4,in p =")
9 Ni/Si CH 4 CH 4 Ni/Si CH 4 Overall decomposition rate constant, k decomp [sec - ] [C] k decomp =3.09x0 exp(-9.5[kj/mol]/r g T) /T [K - ] -CH 4 system Ar-CH 4 system..3 CH 4 C+ CH 4 + * CH 3 * + H* CH 3 * + * = C * + H* C * + * = CH* + H* CH* = C + H* H* = + * k decomp :(/s) k decomp = k F a V k F : x CH4, /x CH4,in x CH4 33 p CH 4, p CH 4,s p CH 4,in p = exp k decomp V CH 4,s W V: 34 Advantages of ceramic fuel cell operated at high temperature Direct energy conversion supplied with CH 4 and O. Endothermic heat can be converted to electricity directly. It can work even when CH 4 is supplied. The temperature condi@on is almost the same with HTGR. The use of Ni can decrease the cost of electrodes. SEM photo and deposi@on of carbon in porous Ni electrode Carbon amount [Atm%] Depsited Carbon (A) Electrode surface (B) Electrode internal (C) Electrode-Electrolyte interface Position Carbon deposi@on profile Direct decomposition might occurred at the interface between electrode and electrolyte. CH 4 + O = CO + 3 Fig. Mass and charge transfer on proton-conducting ceramics cell 35 CH 4 = C +. 36
10 Ceramic fuel cell with CH 4 reformer I- V curves for SrCe 0.95 Yb 0.05 O 3- a ceramic CH 4 + O Ni SrCe 0.95 Yb 0.05 O 3- a NiO + O 37 Cell poten@al, E, can be expressed by a linear curve of E=E 0 - Id/σΑ. EMF, E 0, was correlated by the Nernst equa@on. 38 Proton conduc@vity of SrCe 0.95 Yb 0.05 O 3- a EMF of ceramic fuel cell supplied with CH 4 PEM-FC Nernst equa@on E 0 = ΔG O F R gt F ln p O,cathode 0.5 p,anode p O,cathode + (/) = O + ΔG HO EMF versus O vapor pressure at anode Other protonconducting ceramics Oxygen-conducting ceramics 39 40
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Table 1 Properties of parent coals used Ebenezer, Massel Buluck ; Australia, Datong; China Table 2 Properties of Various chars CY char: Captured char
Table 1 Properties of parent coals used Ebenezer, Massel Buluck ; Australia, Datong; China Table 2 Properties of Various chars CY char: Captured char by cyclone char: Carbonized char at 1273 K 気流 層 石 炭
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SUMMARY Although the situation where sufficient food was not supplied for the victims occurred in the Great East Japan Earthquake, this is a serious problem at the time of catastrophic disasters like the
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;~ (Summary) The Study on the Effects of Foot Bathing on Urination Kumiko Toyoda School of Human Nursing, University of Shiga Prefecture Background Foot bathing is one of the important nursing care for
Fig. 3 Flow diagram of image processing. Black rectangle in the photo indicates the processing area (128 x 32 pixels).
Fig. 1 The scheme of glottal area as a function of time Fig. 3 Flow diagram of image processing. Black rectangle in the photo indicates the processing area (128 x 32 pixels). Fig, 4 Parametric representation
Fig. 1 Sampling positions from the ingot. Table 2 Chemical compositions of base metal (%) Fig. 2 (unit: mm) Shape and size of fatigue test specimen. T
Friction welding of ADC 12 aluminum alloy diecastings Kazuyoshi KATO* and Hiroshi TOKISUE* Both squeeze and gravity castings of ADC 12 aluminum alloy were friction-welded, using a brake type welding machine.
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CHLAC 1 2 3 3,. (CHLAC), 1).,.,, CHLAC,.,. Suspicious Behavior Detection based on CHLAC Method Hideaki Imanishi, 1 Toyohiro Hayashi, 2 Shuichi Enokida 3 and Toshiaki Ejima 3 We have proposed a method for
Table 1. Shape and smelting properties of chrome ores as delivered. Table 2. Chemical composition of chrome ores (%). Table 3. Chemical composition of
UDC 669.263.1: 669.046.462 The Reduction Process and Reducibility of Chromite with Carbon Hiroshi G. KATAYAMA and Akihiko TANAKA Synopsis: In the present work, various chrome ores and relatively pure chromites
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15 C11-4 Numerical analysis of flame propagation in a combustor of an aircraft gas turbine, 4-6-1 E-mail: tominaga@icebeer.iis.u-tokyo.ac.jp, 2-11-16 E-mail: ntani@iis.u-tokyo.ac.jp, 4-6-1 E-mail: itoh@icebeer.iis.u-tokyo.ac.jp,
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Jpn. J. Health Phys., 52 (2) 55 60 (2017) DOI: 10.5453/jhps.52.55 * 1 * 2 * 2 * 3 * 3 2016 10 28 2017 3 8 Enhancement of Knowledge on Radiation Risk Yukihiko KASAI,* 1 Hiromi KUDO,* 2 Masahiro HOSODA,*
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早稲田大学現代政治経済研究所 ダブルトラック オークションの実験研究 宇都伸之早稲田大学上條良夫高知工科大学船木由喜彦早稲田大学 No.J1401 Working Paper Series Institute for Research in Contemporary Political and Ec
早稲田大学現代政治経済研究所 ダブルトラック オークションの実験研究 宇都伸之早稲田大学上條良夫高知工科大学船木由喜彦早稲田大学 No.J1401 Working Paper Series Institute for Research in Contemporary Political and Economic Affairs Waseda University 169-8050 Tokyo,Japan
EQUIVALENT TRANSFORMATION TECHNIQUE FOR ISLANDING DETECTION METHODS OF SYNCHRONOUS GENERATOR -REACTIVE POWER PERTURBATION METHODS USING AVR OR SVC- Ju
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TOP10 Innovations A triple-junction compound solar module with a conversion efficiency of 31.17%. Source SHARP CORPORATION (
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1 2 3 4 This product (including software) is designed under Japanese domestic specifications and does not conform to overseas standards. NEC *1 will not be held responsible for any consequences resulting
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Studies on Collapse of Wood Cells and Negative Pressure in Cell Lumen by Yoshiaki HATTORI* and Yasushi KANAGAWA** The negative pressure, that is liquid-tension, to cause cell-collapse was estimated with
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Authors' Abstract It in known that the method of feeding powder into split cell affects the adhesion forces of powder beds, especially in fine particle powders. But the effect of the agglomeration phenomenon