Biomass decomposition and Hydrogen Production in Supercritical Water enhanced by Ruthenium(IV) Oxide as a catalyst

Transcription

1 Biomass decomposition and Hydrogen Production in Supercritical Water enhanced by Ruthenium(IV) xide as a catalyst Yukihiro Izumizaki 1), Ki Chul Park 2), Yuu Tachibana 2),Hiroshi Tomiyasu 3) Yasuhiko Fujii 1) 1)Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology 2)Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University 3) Nippon TMI Co., Ltd

2 Biomass is recyclable fuel source

3 ecomposition ratios and gas distributions for organic compounds in the presence of Ru 2 catalyst in supercritical water rganic compounds Carbon conversion(%) /C ratio Product distribution(%) CH4 C2 H2 Naphthalene Polyethylene Polypropylene Porystylene PET cellulose Ki Chul Park and Hiroshi Tomiyasu. (2003), Chem. Commun

4 Mechanism of the gasification catalysis by Ru2 Hydrogen produced from water Existence of Ru2+ was confirmed by the UV absorption spectrum

5 Experiment Gasification of biomass in SCW using Ru 2 as a catalyst Experiments were carried out for the following samples Cellulose and lignin (main compounds of biomass) Real biomass Pulp (main sample used in this experiment) Paper sludge and recycled paper (real biomass waste) from Tomoekawa Paper Company Paper sludge recycled paper

6 Experimental procedure Reactor(INCNEL625) Sample Catalyst Water Reaction Finish Reaction,Turn off the Heater Cooling reactor to room temperature Bulb Attachment Connection reactor with Glass line Replacement air to Argon(1h) Connection Heater,Start Heating Gas sampling Achievement to Reaction Temp Analysis

7 Picture of experimental apparatus(1) Reactor Sealing Cap Heater loading slot Thermocouple(heater) and Holder Thermocouple(inside) Heater loading slot(bottom) Sealing Cap(side)

8 Picture of experimental apparatus(2) Valve Gas utlet(connection to Glass Line) Pressure Gauge (for Produced Gases) valve Gas Inlet(Replacement inside air to argon) reactor

9 Picture of experimental apparatus(3) Vacuum Line Vacuum pump Buffer 4 Pressure Gauge (digital) 2 Gas Circulator 5 Reactor and Valve 3 Gas Sampling Cock (Directly Connected to Gas Chromatography)

10 The decomposition ratios for three different samples in the presence or absence of catalyst in SCW Sample SCW SCW+Ru2 Cellulose Pulp Lignin (Sample:100mg Catalyst:20mg Temp:450 o C Time:2h) Unit: % Gas. ratio=100 [C in gas products] / [C in samples loaded]

11 The decomposition of coal and lignin in supercritical water. Sample SCW SCW+Ru2 Lignin Coal(Yallourn) (Sample:100mg Catalyst:20mg Temp:450 o C Time:2h) Unit: %

12 Structures of coal and lignin Bituminous coal lignin H H H H H H H H S H H H N NH 2 H N H H H H H H 3 C H HH 2 C C CH 3 H CH 2 H HC H CHH CH 3 H HC 3 C CH 3 HC H 3 C CH 3 CH 2 H HC C CH H 3 C H CH 2H CHH HH 2 C CH HC H 3 C H H 3 C H CH 3 C HC CH 2 H CH CH 2 HC CH HC CH CH 2 H H 3 C CH CH H 3 C CH 2 H HC CH H 3 C HC CHH CH 2 H CH CH H C CH CH 2 H H HH 2 C CH 3 H H 3 C H C H C H C CH CH CH H H 2 HC C C CH CH C H H C C CH 2 CCHCH H 3 C C CH CH 2 H CH 3 CH 3 HC CH CH 2 H H 2 C CH H HC CH HC C H HC CH H 3 C CH 2 H HC CH CH CH 3 H H 3 C CH 2 H HC CH 2 CH HC CH HC H 2 C CH CH 3 H 3 C H H 2 C C CH CH 4 H CH 3 H 3 C HC H C CH 2 H H CH 3 H CH 2 H CH CH CH 2 H CH CH HC H CH 3 CH 3 CH 2 H C H CH 3 H CH 3

13 Gas species produced from each samples C 2 50 C 2 Propane 40 Ethane % 30 CH 4 H 2 Methane Carbon Dioxide 20 CH 4 CH 4 C 2 Hydrogen 10 H 2 H 2 0 Cellulose Pulp Lignin sam ple produced gas Cellulose Pulp Lignin Methane Ethane Propane Carbon Dioxide Hydrogen Unit:% Hydrogen ratio for other organic compounds Nap hthalene Polyethylene Polypropylene Porystylene Hydrogen

14 Gas species produced from paper sludge and recycled paper % CH 4 C 2 CH 4 C 2 H 2 Propane Ethane Methane Carbon Dioxide Hydrogen 10 H 2 0 Recycled paper Paper sludge sam ple produced gas Recycled paper Paper sludge Methane Ethane Propane 0 0 Carbon Dioxide Hydrogen Unit:% (Sample:100mg Catalyst:20mg Temp:450 o C Time:2h)

15 Volume of gas(ml) produced from 1g of pure cellulose, pulp, paper sludge and recycled paper samples produced gases Cellulose Pulp Paper Sludge Recycled Paper CH 4 321ml 190ml 86ml 233ml H 2 137ml 115ml 87ml 120ml Gas volume at the standard condition [0 o C(273K), 1atm(10 5 Pa)] Confirmation of production of fuel gases such as methane and hydrogen in the case of real biomass waste. This method is available about disposing of wastes

16 Treatment of industrial wastes from paper company Paper sludge Recycled paper rganic residues are negligible This method enables to decompose waste containing biomass.

17 Effect of temperature on the productions of gasses from pulp Amount of Gas(ml) 75 Decomposition(%) Temperature( o C) (Sample:100mg Catalyst:20mg Time:2h) (Gas Volume at the standard condition) [0 o C(273K), 1atm(10 5 Pa)] 50 Carbon Dioxide Hydrogen Methane Decomposition Ratio

18 Comparisons of each gas compositions by changing water volume Amount of Gas(ml) 75 Decomposition(%) Amount of loaded water(ml) 50 Carbon Dioxide Hydrogen Methane Decomposition Ratio (Sample:100mg Temp:450 o C Time:2h) (Gas Volume at the standard condition) [0 o C(273K), 1atm(10 5 Pa)]

19 Mechanism of the gasification catalysis by Ru2 C + 3H 2 CH 4 + H 2 2C + 2H 2 CH 4 + C 2

20 Influence of reaction time on biomass decomposition Amount of Gas(ml) 70 Decomposition(%) Reaction Time(hour) 50 Carbon Dioxide Hydrogen Methane Decomposition Ratio (Sample:100mg Temp:450 o C catalyst:20mg) (Gas Volume at the standard condition) [0 o C(273K), 1atm(10 5 Pa)]

21 Change in gas composition versus the amounts of catalyst(10 mg and 20mg) Amount of Gas(ml) Decomposition(%) Amount of Ru2 catalyst(mg) 40 Carbon Dioxide Hydrogen Methane Decomposition Ratio (Sample:100mg Temp:450 o C Time:2h) (Gas Volume at the standard condition) [0 o C(273K), 1atm(10 5 Pa)]

22 XRD pattern of Ru2 catalyst after reaction XRD pattern of catalyst after reaction Pulp 100mg Catalyst 20mg Reaction temperature 450 o C Reaction time 2hours XRD pattern of purchased Ruthenium powder After the reaction, Ru 2+ (or Ru 4+ )was reduced to Ru as the final oxidation state of ruthenium.

23 XRD pattern of Ru2 after exposure to supercritical water XRD pattern of catalyst after exposure it to supercritical water Catalyst 20mg Reaction temperature 450 o C Reaction time 2hours XRD pattern of purchased Ru2 powder Ru2 is not turned into Ru without catalytic reaction.

24 Comparison of catalytic reactions between Ru 2 and Ni for the decomposition of biomass Ru 2 (450 o C) Ru 2 (500 o C) Methane Hydrogen Gasification ratio 190ml 115ml 71.3% 118ml 202ml 72.4% Ni(450 o C) 147ml 139ml 50.1% (Sample:100mg of pulp Catalyst:20mg(Ru 2 )/40mg(Ni) Time:2h) Each rganic residues after reaction Amount of gas(ml) produced from 1g of pulp [0 o C(273K), 1atm(10 5 Pa)] Ni(450 o C) Ru2(450 o C)

25 Comparison of catalysts between Ru 2 and Ni for the gasification of naphthalene Gasification ratio Ru 2 (450 o C) 96.7% Ni(450 o C) 26.3% (Sample:100mg of Naphthalene Catalyst:20mg(Ru2)/40mg(Ni) Temp:450 o C Time:2h) Ru 2 is much stronger catalyst for the treatment of rganic compounds than Ni

26 The relation of nuclear plant Sun light Product gas C2 CH4 H2 Exploitation as Fuel photosynthesis (Exothermic heat) Plant Biomass (Waste Plastic) SCW Reactor ( o C) (Catalytic reaction in SCW) Exhaust heat (to sustain supercritical condition) Nuclear reactor nuclear plant Available temperature range* HTTR: o C LWR: o C Fast reactor: o C *HTTR homepage

27 Conclusions The present method using Ru 2 as a catalyst in SCW enables to decompose biomass and to produce fuel gases. The gases produced are H 2, CH 4, and C 2 Hydrogen production ratio increases with temperature up to 22.1% at 500 Ru 2 catalyst is superior in catalytic efficiency to other catalyst such as Ni catalyst for decomposition of organic compounds.