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Dr. Razima Souleimanova, GTI Mark Ritter, Xcel Energy
Direct Hydrogen Production From Biomass Gasifier Using H2 Selective Membrane Michael Roberts, GTI Dr. Razima Souleimanova, GTI Mark Ritter, Xcel Energy Dr. Donald Fosnacht, NRRI David Hendrickson, NRRI NHA Annual H2 Conference, March 31, 2008 Sacramento, CA
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Project Objectives Develop a novel membrane reactor process for hydrogen production from biomass gasification Develop hydrogen-selective membrane compatible with biomass gasification Demonstrate the feasibility of the concept in a downdraft biomass gasifier 2
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Project Overview Project Sponsor: Xcel Energy
Project Team: Gas Technology Institute (GTI) Natural Resources Research Institute (NRRI) University of Minnesota at Duluth 3
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Hydrogen Production Cost from Biomass Gasification
Total cost breakdown Capital cost breakdown 4
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Conventional Hydrogen Production from Biomass Gasification
cleaning Biomass Feed preparation Syngas Biomass Syngas Platform CO Syngas Shift reaction 2 PSA Hydrogen removal Tail gas Steam or Power H2 From Syngas generation 5
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Biomass Syngas Platform
Technical Approach - Use high temperature H2-selective membrane for hydrogen separation Gasification Gas cleaning Biomass Feed preparation Syngas Biomass Syngas Platform Syngas Shift reaction Membrane Hydrogen CO2-rich gas Steam or Power H2 From Syngas generation 6
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Biomass Syngas Platform
Technical Approach - Combine shift reaction and hydrogen separation into one membrane reactor (future) Gasification Gas cleaning Biomass Feed preparation Syngas Biomass Syngas Platform Syngas Membrane shift reactor Hydrogen CO2-rich gas Steam or Power H2 From Syngas generation 7
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Biomass Gasifier With Internal or Close-Coupled Membrane Integrated with PEM Fuel Cell
Hydrogen Oxygen/steam Biomass Gasifier PEM Fuel Cell power Membrane CO2 +impurities 8
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Scope of Work Identify and select the candidate membrane
Construct a hydrogen permeation cell unit Install, instrument and shake down a down draft biomass gasification unit Test the hydrogen permeation unit under simulated gas conditions Integrate and test hydrogen permeation unit and the down draft biomass gasifier 9
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Identify and Select Candidate Membrane Materials
Evaluated Pd-Cu and V membranes Fabricated Pd-coated V membranes Developed sealing techniques, 350ºC Determined Effects H2S, CO on membrane permeation Selected V-membrane for initial scale-up Required front-end sulfur removal unit 10
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Laboratory Membrane Testing Unit
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High Temperature Metallic Membranes for Biomass Gasification Application
Driving force: H2 partial pressure Separation based on hydrogen diffusion through the interstitial lattice of metals 100% selective to hydrogen Hydrogen at H 2 2H low pressure high pressure 12
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Permeability of Hydrogen in Different Metals
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Comparison of Hydrogen Fluxes for Pd-coated V Membranes and Pd-Cu Alloy Membranes at 350ºC
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Effect of CO on Pd-Coated Vanadium Membrane
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Effect of H2S on Pd60-Cu40 Membranes
350ºC, 100 ppm H2S 16
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Effect of H2S on Pd80Cu20 alloy membrane at 750-850°C
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Identify and Select Candidate Membrane Materials
Pd-plated V membranes were initially chosen as candidates for testing. Small effect of CO on membrane performance at high feed pressure at 350ºC H2S affects membrane performance dramatically at low temperatures – need front-end sulfur removal unit 17
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Construct a Hydrogen Permeation Cell Unit
Selected planar design for easy membrane fabrication Evaluated membrane support system Evaluated membrane sealing system Conceptual design of membrane module Sized membrane module from process modeling Membrane module fabricated 18
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Cross-Sectional View of the Membrane Cell Design
feed hydrogen Membrane Porous support Copper seal coated by carbon 19
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High Pressure Permeation Testing with Support
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Fabricated Membrane Module
Total active membrane area: 100 cm2 Assembled module dimension: 13 cm x 7.9 cm x 5.8 cm Feed/exhaust plate Product off-take plates Membrane foil Porous stainless steel 21
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Assembled Membrane Module
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Membrane Scale up 7.6 x 12.7 cm 5.1 x 10.2 cm 2.54 x 5.1 cm 2.54 cm 23
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Construct a Hydrogen Permeation Cell Unit
Planar design for easy membrane fabrication Evaluated membrane support system Porous stainless steel (20 µ pores) chosen as substrate due to good mechanical stability. Evaluated membrane sealing system Copper gaskets coated with carbon Membrane module fabricated Scale-up of membrane (2 x 50= 100 cm2) 24
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Install, Instrument and Shake Down a Down Draft Biomass Gasification Unit
Feed Stock Preparation Woody and agricultural (pelletized) biomass Gasifier Installation Purchased a new biomass gasifier (instead of retrofitting an existing one) Commissioning Conducted by NRRI with assistance from GTI 25
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Primary Reduction Zone 815ºC
Downdraft Biomass Gasification biomass Drying Zone 65ºC Tar Formation 230ºC air/ steam air/steam Oxidation Zone 1100ºC Primary Reduction Zone 815ºC gas Ash temperature 26
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Characteristics of Downdraft Gasification of Biomass
Advantages Simple construction Very little tar in product gas High rate of carbon conversion Disadvantages Lump or block size of feed Requires low moisture content of fuel Difficult to scale up 27
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NRRI Biomass Downdraft Gasifier
Manufactured by Community Power Corporation 35 kg/hr feed or 0.24 Giga-joules/hr Footprint: 5 m x 5m Gas composition (~) H2: 15-20%, CO: 20%, CO2: 10%, CH4: 4-5%, bal N2 28
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Operating Data and Producer Gas Composition
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Install, Instrument and Shake Down a Down Draft Biomass Gasification Unit
Approximately 30 tonnes of Northern Minnesota wood chips were procured for use during the commissioning and operation of the gasifier Gasifier was operated hrs/week for a 6-7 week period during shakedown 31
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Tested Hydrogen Permeation Unit Under Simulated Gas Conditions
Tested the new permeation unit under a controlled laboratory environment before shipment to NRRI. 32
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Scheme of permeation unit
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Carbon Bed, WGS Reactor and Booster Compressor
Booster with Surge Tanks 34
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Picture of Assembled Membrane Modular Unit
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Test Hydrogen Permeation Unit Under Simulated Gas Conditions
Pd-plated V membranes replaced by Pd-Cu alloy membranes Tested permeation unit using syngas mixture typical to biomass gasification H2 was extracted from simulated producer gas mixture 36
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Integrated Testing of Hydrogen Permeation Unit and Down Draft Biomass Gasifier
A slip stream from the downdraft biomass gasifier for the feed of the permeation unit ~ 17 sm3/hr syngas, or 200 cc/min H2 Engine to consume excess syngas Continuous operation up to 5 days Full product gas characterization and gasifier performance assessment Demonstrate hydrogen production from biomass syngas Identify future development needs for membrane 37
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Integrated Testing of Gasifier and Membrane Unit
NRRI Prepare a slip stream from biomass gasifier Operate the gasifier Assist with some analytical & mechanical work GTI Install membrane unit Operate membrane unit Evaluate membrane performance 38
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Flow Diagram of Membrane System for Integrated Testing with NRRI Biomass Gasifier
steam Nonpermeate syngas carbon bed compressor Hydrogen shift reactor heater Membrane module A slip stream of syngas from biomass gasifier 39
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Permeation Unit is Processing
Product Gas Using Slip Stream from Gasifier. Slip stream Vacuum pump Permeation Unit 40
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Gas Analysis Equipment
NOVA Analytical system Micro GC Bubble meter 41
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Conclusions Pd-Cu alloys were selected as membranes for hydrogen permeation in biomass-derived syngas environment Membrane module capable of operating up to 500ºC and 30 bar was designed, built and commissioned. Permeation cell with carbon bed, water-gas shift reactor, booster and membrane module was constructed to increase efficiency of hydrogen extraction from producer gas (up to 70% efficiency) Integrated testing of permeation unit with biomass gasification was successfully conducted Demonstrated feasibility of hydrogen separation from producer gas obtained by biomass gasification using a membrane 42
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Acknowledgements Xcel Energy, MN
Natural Resources Research Institute (NRRI) at University of Minnesota at Duluth 43
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