Fuel Flexible Reformers for Stack Integrated Systems and H2/Syngas Generation

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1 Fuel Flexible Reformers for Stack Integrated Systems and H2/Syngas Generation Subir Roychoudhury VP Research and Engineering

2 Precision Combustion, Inc. Technologies Microlith Catalytic Reactors, and RCL Combustors Reforming: Syngas, H 2, Chemicals, W MW scales Sorption: Bio/Chem, Sulfur, trace contaminants Small Generators: Tactical Power, UAV Combustion: Gas turbines, burners, augmentation, down-hole, Stirling Prototypes: BOP, Controls, packaging 38,000 sq ft facility Established 1986; Privately held, Small Business; 34 employees; North Haven, CT USA Collaborators include: U.S. Govt., large & small corporations, universities, national labs. Develop advanced catalysts, reactors/systems; manufacture limited-volume units 2

3 Product Applications Power Combustion Air Cleaning Other Fuel Cell Systems APUs/Gensets Vehicles/Ships Kitchen Burner Oxidizers H2 generation for compact GTL IC Engines Tactical Gensets Stirling Burner Adsorbers Catalytic ignitors UXV Fuel Cell Systems Fuel Cell System Oxidizers Desulfurization Power-to-Gas Sabatier Methanation Reformers for Industrial Systems Catalytic Combustors Combustors Steam generators Chemicals manufacture Shale Gas to Chemicals Engineering Services 3

4 Reforming (for Fuel Cells, H 2 Gen, Comb. Aug.) 1. Catalytic Partial Oxidation (CPOX) 2 CH 4 + O 2 4 H 2 + 2CO {H 2 O + CO 2 - H} 5 kwth Diesel For Automotive 5 MWth Nat. Gas 2. Catalytic Autothermal Reforming (ATR) 3 CH 4 + O 2 + H 2 O 7 H CO {H 2 O + CO 2 - H} 5 kwth Diesel/JP-8 ATR Module 1 MWth Liquid HC Reformer 3. Catalytic Steam Reforming (CSR) CH 4 + H 2 O 3 H 2 + CO {H 2 O + CO 2 + H} 3-10 kwth Diesel SR- Exo/Endo sections Application specific reformers, using its Microlith Technology 4

5 H 2 Purification Water Gas Shift Reactor (WGSR) CO + H 2 O H 2 + CO 2 {CH 4 - H} Preferential Oxidation of CO (PROX) CO + ½ O 2 {H 2 } CO 2 {H 2 O - H} Membrane Separation Integration Pd/Ag/Polymer on metal/ceramic supports HT-PEM and LT-PEM Quality Reformate Generation 5

6 PCI Innovation: Diesel/Jet-A Reformer with Sulfur Cleanup Ultra-compact, high efficiency, water-neutral reformer for producing stack-quality reformate Reformer includes catalyst, steam generator, HX, sulfur cleanup, fuel/air/steam mixer, igniter Value: Allows SOFC s to use diesel/military fuels (up to 3,000 ppmw Sulfur) With PCI s WGS, allows HT-PEM fuel cells to use diesel/military fuels With H 2 separation, demonstrated to produce PEM quality hydrogen 100 We 1 kwe 1 kwe High Sulfur 2 kwe 10 kwe 300 kwe We put the fuel in fuel cells 6

7 Microlith ReactorTechnology Conventional Monolith Microlith Cells/in 2 GSA (m 2 /l) Channel Length (in) Length to Diameter Ratio (L/d) Operating Temperature ( o C) Frontal Open Area Monolith wall Mixing regions Boundary layer formation Monolith wall Boundary layer formation Monolith wall High surface area & high mass/high heat transfer capability at comparable pressure drop 7

8 Microlith Reactor Technology Small, durable, catalytically coated metal mesh with very high surface area Microlith Catalytic Reactors Ultra compact Short contact time Rapid thermal response High heat & mass transfer High surface area/unit volume Low cost Continuous catalyst coating line with batched furnace and rigorous QA, QC in place PCI holds multiple patents on catalyst structure, reaction methods and apparatus 8

9 Comparison of Substrate Performance (Steady State Operation w. propylene in air at 350 C, vel. 1.5 m/s.) 2.54 cm(1 ) long monolith 7 Microlith elements (Length = 0.11cm, ) 5.3 cm/s 7620 cm 2 75 Mass Transfer Coeff (k c ) GSA Observed Conversion (%) 77 cm/s 568 cm 2 78 Equivalent conversion with 20-fold size reduction. More Efficient Use of Catalyst Surface Area 9

10 CPOX: 5 MW(th) Natural Gas Processor 5 MWth reactor to reform natural gas to produce syngas Performance testing successfully completed hrs of sub-scale durability completed. 10

11 ATR Reformate Compositions (mole %, wet basis) F/A/S Atomizer ATR HEX Sulfur Trap WGSR Fuel S/C O/C H 2 O H 2 N 2 CO CO 2 CH 4 C2 + C3 S JP-8 (Equil) JP-8 (Exptl) <50 ppm <1 ppm After WGSR <1 * [*: Fn of St/C] Reforming efficiency (LHV reformate/lhv feed) = ~85% Sulfur removal to <1 ppm Current PCI s target for coke precursors (i.e., C2s and C3s) is <50 ppm v total 11

12 Sulfur Tolerant Reforming ATR performance and durability testing w. 400 ppmw sulfur Jet-A at S/C of ppm w Sulfur Jet-A O/C = variable (closed-loop); S/C = 0.90 Complete fuel conversion, stable LHV-based efficiency & H 2 +CO mole % over time. Total organics (primarily C2, C3) <100ppm at end of test. Fuel-bound sulfur converted to H 2 S and removed (<1 ppm) downstream of reforming reactor Total sulfur analysis: ASTM D2622 (Wavelength Dispersive X-Ray Fluorescence) ~360 ppmw sulfur (Sulfur speciation: ASTM D5623) 12

13 PCI Designs/Supports Complete Stack Integrated Systems é Fuel Processor (ATR, injector, steam generator, sulfur trap, igniter, fuel & water pump, air blower, fuel/air/water control) Reformate Flow Thermal balance Control SOFC (Stack, cathode air blower, Power conditioning, stack controller, AGB) Fuel, Air, Water Capable of Startup, load-following, shutdown 13

14 Fuel Flexibility, BOP, System Integration, Packaging Convert diesel, Jet fuels, alcohols, biofuels, gaseous fuels to sulfur-free syngas Fueling for SOFC s, HT-PEM and LT-PEM Implementation of: commercially available Pumps, Blowers Flow controllers, Sensors Microlith based compact catalytic burners (startup/anode exhaust) Heat exchangers Water recovery Steam generators Control hardware/software, and algorithms Complete Generator Packaging (stationary, mobile) PID, PFD, Haz-ops (Safety certifications, Operating Procedures) Manufacturing Support (Engineering Drawings) Leverage Small Size and Commercial Off The Shelf Hardware for Low Cost. 14

15 Test Carts to Enable Complete System Testing Mass Flow Controller based test systems Embedded control software to enable push-button operation Data acquisition and analysis capability included BOP components included (steam generator, water recovery and recycling, burner, etc.) Can be integrated with different types of stacks Enables controlled testing of stack and reformer systems Gas sampling system 15

16 Commercial Applications Aircraft APU Truck APU Marine APU Fuel Cell Range Extenders RV APU Industrial Syngas 16

17 Scale-up: 1 MW th ATR System Injector 63 ATR Igniter Steam Generator 6.8 ft Trim HEX WGSR Desulf. 48 Modular Fuel Processing System consisting of fuel/air/steam injector, ATR steam generator hex, sulfur clean-up, controls, pumps, blowers, filters, sensors. 17

18 Scale-up: 1 MWth VOC Reformer Microlith ATR for reforming VOC compounds from process waste streams 18

19 Turnkey Syngas Generation Units Oxygen Blown Syngas Generators Operating on Natural Gas Over 4,000 combined operating hours to date making over 50,000 Nm 3 syngas 19

20 7 10 kwth SR for Diesel, Natural Gas Low peak temperatures Sulfur tolerance (~5 ppm) High Heat Flux Compact size Capable of high pressure operation Achieves thermodynamic efficiency at Low S/C ratios Catalytic burner instead of flame-stabilized burner increases thermal uniformity, distribution, durability & control. 20

21 SR Reactor Test Summary 500-hr durability testing successfully completed Stable SR reformate w. ~70 mol% H 2 (dry basis) Complete fuel conversion to C1 products Product composition in good agreement w. thermodynamic equilibrium prediction Operated both SR & burner w. GTL (2-5 ppm w sulfur) for 450 hrs (50 hrs w. n-c12) SR Exptl. data vs. Thermodynamic equilibrium Exptl Product Mol%, S/C=3.0, P = 1 atm Equilibrium Mol%, S/C=3.0, 1 atm H CO CO CH kw th ~ 8 SLPM of H 2 i.e., 0.96 kg H 2 /day LHV-based efficiency ~119% (synfuel) 115% Durability testing w. GTL (2 5 ppm w Sulfur) 21

22 H 2 Generator Heat Fuel + Water Steam Reformer Reformate Membrane Permeate (UPH) N 2 as internal standard H 2, CO, CO 2, CH 4, H 2 O, N 2 Raffinate H 2 CO CO 2 CH 4 H 2 O N 2 Avg. Reformate composition (mole%, dry basis) Reformate flow rate (SLPM) Raffinate composition (mole%, dry basis) Raffinate flow rate (SLPM) H CH CO CO N (Separation Efficiency, %) UPH (SLPM) Reformate H (SLPM) % H 2 Generation rate of ~17 slpm

23 Sabatier Methanation Reactor Sabatier reaction CO2 + 4H 2 CH4 + {2H 2 O - H} Demonstrated at laboratory scale Compact unit with less pressure drop than pellets or foams Suitability for Power to Gas Systems 23

24 Come See Us! Precision Combustion, Inc. Booth# C40/3 We put the fuel in fuel cells Subir Roychoudhury VP Research and Engineering Ext.267 Tony Anderson Director, Marketing & Business Development Ext