Development of the Highly Durable COS Hydrolysis Catalyst for IGCC Gas Clean-up System

Development of the Highly Durable COS Hydrolysis Catalyst for IGCC Gas Clean-up System Mitsubishi Heavy Industries, Ltd. Kaori Yoshida 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. October 31, 2012

Outline Update of Nakoso Demonstration Plant MHI IGCC System MHI Gas Clean-up System Characteristic of MHI COS Hydrolysis Catalyst Results of Demonstration Test 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 1

250MW IGCC Demonstration Plant (Nakoso) 140m HRSG GT / ST 140m Gasifier Gas Clean-Up METI 30% Subsidy 70% Contribution Clean Coal Power R&D Co., Ltd. Ministry of Economy, Trade and Industry Joint Project Agreement Researchers Hokkaido EPCo. Tohoku EPCo. Tokyo EPCo. Chubu EPCo. Hokuriku EPCo. Kansai EPCo. Chugoku EPCo. Shikoku EPCo. Kyushu EPCo. J-Power CRIEPI Nakoso Tokyo MHI Single Point Responsibility (EPC Turn-Key Contract) Power Plant Section Chemical Section 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 2

250MW IGCC Demonstration Project (Nakoso) 2007 ~ 2010 Project execution went on Schedule. Operation started Sep. 2007 100% Load 2,000hrs. Continuous Operation completed (2008) Various testing activities Coal Change / Load Swing / Efficiency Improvement, etc. 5,000hrs. Durability Test completed Subsidy from METI ended 2011 ~ Coal Change / Load Swing / Efficiency Improvement, etc. 18,000 hrs. Operation 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 Engineering Construction Operation 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 3

Targets & Achievement of Demo. Plant Targets Achievements Note Performance Output 250MW 250MW Efficiency (Net, LHV) > 42.0% 42.9% Carbon Conversion > 99.9% > 99.9% Emission (@dry, 16%O 2 ) SOx NOx Dust < 8 ppm < 5 ppm < 4 mg/m 3 N 1.0 ppm 3.4 ppm < 0.1 mg/m 3 N Operational Flexibility Coal tested Bituminous Sub-bituminous Chinese, PRB 3 Indonesian Subs Colombian, Russian Continuously testing other coals Start-up Time < 18 hr 15 hr Minimum Load 50% 36% Ramping Rate 3%/min 3%/min Reliability Long-term Continuous Operation 2,000 hr 2,238 hr Long-term Reliability Run 5,000 hr 5,013 hr All of the demonstration targets have been achieved. Future plan focuses on the further improvement of operational flexibility. 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 4

250MW IGCC Demonstration Plant (Nakoso) Specification Gasifier Dry feed, Air blown, Two-Staged Entrained Bed Gas Clean-up MDEA (Methyl Di-Ethanol Amine) Gas Turbine MHI D-type (1,250ºC Class) Coal feed 1,700 t/day Plant Efficiency 42% (LHV, Net) Emission SOx : 8 ppmv (16% O 2, dry) NOx : 5 ppmv (w/scr) Dust : 4 mg/m 3 N MHI Supplied All the Key Components 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 5

MHI IGCC System 石炭 Coal Pulverizer SGC (Syngas Cooler) from/to HRSG Gas Treatment Gas Clean-up Section Heat Recovery Steam Generator Hopper Gasifier Gas Turbine Air to/from SGC Slag Hopper Gasification Section Compressor Steam Turbine Transformer 変圧器 Combined Cycle Section 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 6

Each Section of MHI Gasification Section Gasifier Gas Clean-up Section Combined Cycle Section Gas Turbine Steam Turbine for Power Plant Remove impurities and purify the raw syngas. Impurities : H 2 S, COS, NH 3, HCl, HCN and etc. Impurities cause corrosion problem Use chemical wet scrubbing to purify (ex. MDEA) 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 7

MHI Gas Clean-up System Syngas from Gasifier Purified gas GGH* *Gas-to-gas Gas Turbine Sulfur Product COS H 2 S COS Converter Heat Exchanger COS Hydrolysis Catalyst Stack Sulfur Recovery System Effluent Furnace GGH* Wastewater Treatment Sludge Off-gas Washing Tower H 2 S Absorber H 2 S Stripper MDEA Solvent Waste water NH 4 + Cl - 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 8

COS hydrolysis reaction COS + H2O H2S + CO2 ( COS + H2 H2S + CO ) COS can t be removed with amine solvent, it needs to convert to H2S with COS hydrolysis catalyst. HCN + H2O NH3 + CO HCN hydrolysis reaction is also occurred at the same operating condition as COS hydrolysis catalyst. * HCN : Deadly poison gas in gasification raw syngas 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 9

Characteristics of MHI catalyst 1. High durability against impurities in syngas High durability against halogen, COS hydrolysis catalyst fit in front of halogen removal system. 2. High COS hydrolysis performance at high temperature Reaction temperature: 300 ºC (572 ºF) 3. Low pressure drop and less plugging Honey-comb shaped module 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 10

Honey-comb shaped catalyst Low pressure drop and less plugging Honey-comb shaped module Less plugging than pellet typed catalyst Many experiences of MHI SCR honey-comb shaped catalyst 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 11

History of the catalyst development R&D has been carried out step by step to commercialize the new catalyst Commercial 3,600tpd Evaluation by MHI 24T/D Pilot Plant Demonstration Test Scale-up 1,700tpd Pilot Test (Honey-comb shaped) 24tpd Labo. Test @ Hiroshima R&D Center 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved.

History of the catalyst development Testing more than 18,000 hr at Demo. Plant Changing the load of the plant Syngas from several types of coal The demo. plant is now in operation and the catalyst test still continues Commercialize the catalyst Commercial 3,600tpd MHI catalyst is ready to offer for commercial IGCC plant Pilot Test (Honey-comb shaped) 24tpd Labo. Test @ Hiroshima R&D Center Demonstration Test Scale-up 1,700tpd HRSG GT / ST Gasifier Gas Clean-Up 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. Evaluation by Nakoso Demo. Plant

Results of Demo. Test (~16,000hr) @Nakoso The measured value is consistent with prediction from rate equation High COS hydrolysis performance with 1~100 ppm halogen in syngas No replacement of the catalyst from 2007~present Syngas from several types of coals have tested HCN Conversion : > 99% 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 15

Comparison of Gas Clean-up System (a)conventional system Syngas To GT Re-heating COS Converter H2S Absorber Water wash (decrease temp.) Scrubber 150ºC 302ºF Remove dust and halogen Washing Tower (b)mhi system Syngas To GT COS Converter Minimize heat loss H2S Absorber 300ºC 572ºF Washing Tower 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 16

Waste Water Treatment (a)conventional (ex.) Chemical Ozone Chemical Steam Waste Water Ca and F removal Cyanide oxidation Heavy metals removal Evaporation (b)use of MHI COS hydrolysis Catalyst Chemical Chemical Salt Steam Waste Water No cyanides Ca and F removal Heavy metals removal Evaporation Improve OPEX and CAPEX Safe process (no cyanides) Salt 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 17

Summary Advantages of MHI Catalyst Process Pressure drop Waste water treatment Plant efficiency MHI Simple Honey-comb 〇 No cyanide Excellent Other Complex Pellet 〇 Good There are many advantages of MHI Catalyst 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 18

Conclusion Nakoso IGCC demo. plant is now in operation and all of the targets have been achieved COS hydrolysis performance is confirmed from 18,000 hrs demonstration test MHI designed gas clean-up system minimizes the energy loss and provides highest reliability MHI offers COS Hydrolysis Catalyst based on our own technology. 2012 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 19