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Treating Coal-Bed Methane Produced Water for Beneficial Use by MFI Zeolite Membranes Contract #: DE-FC26-04NT15548 Project term: 10/01/04 ~ 09/30/07 Principal Investigator: Junhang Dong Project Manager: Robert Lee Petroleum Recovery Research Center Petroleum and Chemical Engineering Department New Mexico Tech, Socorro, NM 87801 Ph: (505) 835-5293; Fax: (505) 835-5210; Email: jhdong@nmt.edujhdong@nmt.edu Program Manager: Jesse Garcia NETL/DOE, Tulsa April 17, 2004 Slide 2 THE RESEARCH GROUP Justin Monroe, Ben Brooks, Marlene Axness, Alex Bourandas, Junhang Dong, Rich Zhang, Theo Hosemann Xuehong Gu, Liangxiong Li, Colin Edwards, Ani Kulkarni, Chunkai Shi Spring 2005 Slide 3 1% PW, 1,800ppm 100% PW, 180,000ppm 10% PW, 18,000ppm 0% PW 1% PW, 1,800ppm 100% PW, 180,000ppm 10% PW, 18,000ppm Grass Alfalfa From Brittni Romero (Socorro middle school), NM State Science Fair 2005 Hobbs oilfield PW 180,000ppm; Farmington CBM PW 18,000ppm. (Hobbs) (~CBM) Slide 4 Gas-field & Oilfield Produced Water Clean Water Concentrated Prod. Water CBM Produced Water Management Challenge and Our Strategy Disposal, e.g. deep well injection (costly) SEPARATION (Beneficial uses) Challenge: Lacking of technology for efficient SEPARATION Goal of this project: Reverse osmosis purification of CBM produced water by molecular sieve zeolite membranes Slide 5 Comparison With Benchmark Polymeric RO Membranes PropertiesPolymer MembraneZeolite membrane Organic resistancePoorExcellent Organic rejectionIncapableofVery good Ion rejection Good Good Applicable TDS levelLow (800 Psi< 450 Psi Thermal stabilityPoorOutstanding Water flux>5 kg/h.m 2 ~0.5 kg/h.m 2 Membrane costLowHigh Slide 6 PROJECT OBJECTIVES PHASE 1: Mechanisms of the reverse osmosis process on zeolite membranes and factors determining the membrane performance (10/04 ~09/05) PHASE 2: Membrane improvement and operating condition optimization to enhance water flux and ion rejection (10/05~09/06) PHASE 3: Long-term reverse osmosis operation, data generation, and evaluations of technical and economic feasibilities (10/06~09/07) GO/NO GO point Slide 7 SCHEDULE Task YEAR 1YEAR 2YEAR 3 Q1Q1 Q2Q2 Q3Q3 Q4Q4 Q1Q1 Q2Q2 Q3Q3 Q4Q4 Q1Q1 Q2Q2 Q3Q3 Q4Q4 Subtask 1.1. Synthesize and improve zeolite membranes Subtask 1.2. Water and ion transport mechanisms Subtask 1.3. Effects of operating conditions Subtask 2.1. Membrane modification in simple solutions Subtask 2.2. Membrane modification in produced water Subtask 2.3. Stability of modified membrane Subtask 3.1. Build 0.1-m 2 membrane unit Subtask 3.2. Long-term operation test Subtask 3.3. Technical and economic evaluations ???? Subtask 3.4. Final report Slide 8 Research Progress (PHASE 1) SUBTASK 1.1 Synthesize and improve zeolite membranes In-situ growth is better than seed-secondary growth for MFI type (pd = 0.55nm) Seed-secondary growth is better than in-situ for FAU type (pd = 0.74 nm) Synthesis of high quality MFI membranes on commercial tube substrates (Pall Co.) NaY (FAU) membraneSubstrates and DESAL unit MFI membrane Slide 9 Characterization & broader applications NaY for CO 2 /N 2 /H 2 O separation at 200 o C. (Ind. Eng. Chem. Res., 2005) Zeolite framework Pt-Co cluster CH 4 feed H 2 sweep CH 4 CH x H2H2 C 2+ H+H+ Zeolite pore Pt-Co/NaY for CH4 conversion to H 2 and C 2+. (Catalysis Letters, 2005) FAU (NaY) Membranes MFI for separations of xylene isomers. (AIChE J. 2005. In preparation) MFI-fiber integrated sensor for water monitoring. (Optics Letters, 2005) MFI Type Membranes Slide 10 Surface Cross-section Pore dia. ~ 0.55 nm Film of inter- grown crystals Undesirable intercrystal pore Zeolitic pore SUBTASK 1.2 Water and ion transport mechanisms Slide 11 RO permeation mechanism: 1. Rejection size exclusion (high) 2. Lower rejection at intercrystal pores 3. Flux: water and ion diffusivities Ion and Water Transport Through the Zeolite Membrane Separation Mechanism Slide 12 RO desalination for LiCl and NaCl solutions of 2.75MPa. T, o C 0.1 M LiCl0.1 M NaCl r i, %F i, molm -2 h -1 F W, molm -2 h -1 r i, %F i, molm -2 h -1 F W, molm -2 h -1 1099.3 0.52 10 4 3.5797.2 1.26 10 4 3.91 3099.0 0.79 10 4 3.8398.0 2.11 10 4 5.66 5098.8 1.39 10 4 5.9298.7 12.52 10 4 6.44 6098.7 1.89 10 4 7.17 1.3 Effects of operating conditions Slide 13 Mechanism: Theoretical model for ion transport & RO process Ficks Law equation: Modified Diffusion Model (Steps 1+2): Ions entering zeolitic pores: Water entering zeolitic pores: Ion con. Inside pore on feed side: Step 1 selectivity: Ion flow rate: Step 2 selectivity: Overall selectivity: Water flow rate: Slide 14 Effect of inter-crystal pores and membrane modifications (PHASE 2, SUBTASK 2.1) Slide 15 Minor adjustment 1.Economic evaluation (via simulation) earlier ? Received many inquiries about the economic feasibility. 2.Start building the demon unit earlier ? Program status Slightly ahead the schedule Slide 16 Sensor Program at NMT Hai Xiao (PRRC/EE, NMT) Junhang Dong (PRRC/ChE, NMT) Strategy: Strategy: Nanomaterial-enabled optical chemical sensors by interdisciplinary approaches. Challenges: Challenges: Highly sensitive and selective for in-situ and continuous operation. Objective Objective Robust sensors for in-situ detection/monitoring of various chemicals energy industryenvironment protection involved energy industry and environment protection. Slide 17 Sensors for Produced Water Management Approach: Miniaturized sensors by integrating zeolites with optical fibers Objective In-situ monitoring of various organics in produced water 10ppm Silicalite sensor response to isopropanol concentration in water. MFI (Si/Al=200) sensor response to pentanoic acid in water. (a) 100 m (b) 10 m (d) ~4 m fiber zeolite (c) Slide 18 Sensors for Coal-Firing Power Plants Funded by DOE/NETL (4/1/05 3/31/08) Objective: Develop low-cost, reliable, and miniaturized sensors for in-situ monitoring of gas composition in flue or host gas streams of coal-firing power plants. Challenge: Harsh environment: high temperature, high pressure, and particulates Strategy: Nanocrystalline doped-ceramic enabled optical fiber sensors Drop of polymeric precursor Optical fiber (a) Precursor coating (b) YSZ coated fiber tip Photo of the experimental setup Sensor response to O 2 and N 2 at 500 C One of the proposed sensor structures Slide 19 Sensors for Environmental Monitoring Sensors for in-situ chemical vapor detectionSensors for in-situ chemical vapor detection 100% N 2 Isopropanol (1.3%) in N 2 Sensor response to isopropanol concentration in N 2. Inset: response to gas switching. Sensors for in-situ detection of heavy ions (e.g. Hg)Sensors for in-situ detection of heavy ions (e.g. Hg) Slide 20 Sensors for Hydrogen Infrastructure Planned Work Fiber sensors for hydrogen production and fuel cellsFiber sensors for hydrogen production and fuel cells Real time and in-situ monitoring the chemical compositions to achieve optimal fuel cell operations. Small size for easy deployment/integration. High temperature capability and material compatibility for solid oxide fuel cells. Fiber sensors for hydrogen transportation and storageFiber sensors for hydrogen transportation and storage Continuous monitoring of hydrogen flow and leakage. Remote and distributed operation to pin-point the problem. Passiveness for maximum safety. Slide 21 THANK YOU! S OCORRO NM W ILDLIFE R EFUGE