advanced membrane reactors in energy systems development

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Advanced Membrane Reactors in Energy Systems Development of novel membranes for membrane reactors.

Wim Haije, Daniel Jansen, Cor Peters, Joop Schoonman

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GCEP meeting, Stanford University, June 13-16 2005

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Contents

ECN: an overview of activities

TU Delft: an overview of activities

The project

General

Tasks ECN

Tasks TU Delft

Related R&D results ECN

Related R&D results TU Delft

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ECN: an overview of activities

MissionMission statement :statement :

“ To develop high level knowledge and technologies needed for the transition towards a sustainable energy

supply “

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ECNECN’’s s research research areasareas

Clean conversion of fossil fuels

35%turnover

CFF

Emission Reduction

Climate-Neutral Energy Supply

(DECAFE)

Energy and Environmental

Quality

FCT

Fuel Cell Vehicles

Micro Co-generation

Systems

Renewable Energy

40%turnover

solar

Thin-film PVTechnology

Grid ConnectedPV Systems

Wind

Wind FarmOperations

Wind Farm Design

Wind Turbine-Technology

BMBiomass Co-

firingIn Large Scale

Power Generation

Combined Heat & Power

Fuels and Products

Effic

ient

Use

15%turnover

EEI

MolecularSeparation Technology

Industrial Waste Heat Utilisation

Process Intensification

SEBE

IntegrationDecentralized

systems

10%turnover

PC

Policy Studies

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ECN ECN EnergyEnergy Efficiency in Efficiency in IndustryIndustry

Separation technologyMembranes: dense and porous•Dewatering of organics•Air-separation•Hydrogen membranes

Waste heat technologyHeat pumps: solid sorption, thermo acoustic•Heating•Cooling•Storage

Process intensificationMembrane reactors, hex reactors

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ECN Clean Fossil FuelsECN Clean Fossil Fuels

• System concepts and technology assessments• CO2-capture technologies• H2-technology• Stirling micro-cogeneration• Fuel cell technology i.e. PEMFC and SOFC• Emission reduction• Environmental research

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CO2 capture activities

SOFC components

Ceramic membranes

Sorbents

Sequestration• Mineral-fixation• Bio-fixation

SOFC + afterburners

GT + membrane reformer

Systems Engineering

Sorption enhanced reforming

GT + oxy-fuel

On-site H2 productionmembrane reactor

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TU Delft: an overview of activities

Delft Institute for Sustainable Energy (DISE) coordinates the research on sustainable energy of the Delft University of Technology.

The research program focuses on the production, storage, fundamental aspects and utilization of electrical energy and hydrogen.

Hereto, advanced 3D-nano-structured solar cells and small wind turbines are being studied for de-centralized conversion and also storage of sustainable energy in the built environment. Rechargeable Li-ion batteries are being studied for the storage of electrical energy.

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Sustainable energy sources, like solar and wind energy, can also be stored via electrolysis of water to form hydrogen. Hydrogen, as an energy carrier, can be converted into electrical energy using a fuel cell. The safe storage of hydrogen is a prerequisite for the introduction of a Hydrogen Economy.

DISE’s projects are focusing on:novel nano-structured solar cellsnovel nano-structured functional materials for rechargeable batteriesnovel photo-electrochemical (PEC)cellsintegration of the hydrogen storage concept in PEC-cells

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The GCEP project: General

Objective

The purpose of this project is to develop H2 and CO2 membranes to allow combination of natural gas reforming with H2 or CO2 separation in separation enhanced reactors, i.e. membrane reactors, for carbon-free hydrogen production or electricity generation.

Advantages: • eliminating the requirement of water gas shift reactors: cost reductions; • offering higher conversion efficiencies at lower temperatures; • decreasing primary energy use for CO2 separation/capture in power generation.

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systemstudies

reactordesign

membrane & catalyst

development

materialsresearch

experimentalresults

reactorrequirements

desired specificationsfundamental knowledgecharacterization

overall efficiencieseconomics

reactor testspatentsIP

IPpublications

newdevelopments

Task 1. System analysis and thermodynamic evaluations Task 2. Hydrogen membrane research & development Task 3. CO2 membranes research & development Task 4. Catalyst screening Task 5. Reactor modelling and design

Executed by ECN Executed by TUD Executed by ECN+TUD Executed by ECN Executed by ECN


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Macroporous Support (γ- Al2O3)

Molecular Separation Layer

(IL, microporous, Hydrotalcite)

Intermediate Porous LayerChemical Vapor Infiltration (CVI), and Sol-Gel (1-5 nm)

Outside Reactor Wall with Reaction Catalyst


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Cooperation TUD-ECN:

• Mutual consent on new post docs/PhD: do they fit in the team

• Mutual access to analytical/test facilities

• Joint scientific reporting to GCEP

• Progress meetings: once every 8 weeks


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The project: Tasks ECN

Task 1: System analysis and thermodynamic evaluations• Aspen+/exergy assessments of membrane processes. Sets boundary conditions for operational window of the membranes

Task 3a: CO2 membranes R&D• Material choice (hydrotalcites, calixarenes etc.), characterisation, membrane formation, separation tests, etc.

Task 4: Catalyst screening• Screening of commercial catalysts, kinetics,stability and coke formation

Task 5: Reactor modelling & design• Reactor model development (transport models, hydrodynamics etc) to be used as a “plug-in in Aspen+

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Development of a Nano-Structured Ceramic Membrane for High-Temperature Hydrogen Permselectivity

• Hydrogen production through steam reforming of natural gas:

CH4 + H2O → 3H2 + CO ∆E=206 kJ/mol

The application of high-temperature ceramic membrane reactors to this steam-reforming reaction has the potential to achieve similar conversion efficiencies as those attained in conventional reactors at a significantly lower temperature of about 500ºC.

• Nano-structured ceramic layer for hydrogen separation based on differences in kinetic diameter

catalyst

800ºC

The project: Tasks TU Delft

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Task 2: Hydrogen membranes research and development

•Modify CVD reactor for Chemical Vapor Infiltration and Atomic Layer Deposition

•Materials and Catalyst selection, characterization and membrane formation

•Study steam reforming reaction and in-situ hydrogen separation

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The project:

The Goals are:

1. Thermal stability: T @ 500°C

2. H2 permeability: 10-6~10-5 mol/m2.s.Pa

3. H2 perm-selectivity: α (H2/N2) ~ 1000


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Task 3b: Ionic liquids R&D

•Simulation of thermodynamic,structural and transport behavior

•Quantum chemical calculations to investigate inter-ionic interactions

•Material testing

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Related R&D results ECN•CO2 membrane candidate: Hydrotalcite

CO3-ions

H2O

H2, H2O

Natural gas

Recuperation and/orWaste Heat Use

H2O

AirH2O

Q

Reforming

Pre-Reformer

GT

CO2

H2Membrane

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NG membrane reformer combined cycle

Column ofdistillation

CO2

CH4+H2+CO….

methane

B

HP bfw

MP bfw

LP bfw

C

D

methane

condenser

air

E

E

A

H2O cond

SRMR

PRE REF

AB

• Efficiency with capture 50+ % LHV• Capture ratio > 80%• Permeate combustion looks very attractive


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4

5

6

7

8

9

0 20 40 60 80 100

Cycle number

CO

2 upt

ake/

rele

ase

(ml)

0%

20%

40%

60%

80%

100%

CH

4 con

vers

ion

(%)

adsorbed CO2

CH4 conversion

desorbed CO2

symbols: experiment

dashed line: calculated from thermodynamics without adsorbent present

adsorption conditions: 25 ml/min, 2.9% CH4, 17.5% H2O and 79.5% N2,, 10 minutes; desorption conditions:100 ml/min, 29% H2O, 71% N2,, 75 minutes; sample: 1,5 g catalyst, 3,0 g K-promoted htc

SERP demonstrated for steam reforming of methane at 400 ºC and 1 atm

Conversion: +40%!

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0 50 100 150 200 250

Time [min]

CH4

,CO 2

,CO

con

cent

ratio

n [v

ol%

]

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

CH 4

conv

ersi

on [%

]

desorption desorption desorptionads ads ads ads

CH4

CO2

Conversion

Desorption much slower than

adsorption


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Ionic Liquids:

1-butyl-3-methyl-imidazolium-bis-(trifluoromethylsulphonyl) imide

Abbreviation: [bmim][Tf2N]

NN CH3CH2

CH2

CH2

CH3 SO

OC

F

FF

C

F

F

F

SO

O

N+

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Thermal stability of ionic liquids

254[bmim][Cl]

439[bmim][Tf2N]

452[pmim][Tf2N]

440/455[emim][Tf2N]

150[emim][CF3CO2]

349[bmim][PF6]

375[emim][PF6]

360/403[bmim][BF4]

412[emim][BF4]

265[bmim][I]

Temperature onset for decomposition (dried), °C

Ionic liquid

ref: Huddleston et al. (2001)

Viscosity decreases in the order Cl-> [PF6]->[BF4]->[Tf2N]-

716[hmim][Cl]

314 at 20°C[hmim][BF4]

52[bmim][Tf2N]

—[hmim][Tf2N]

28[emim][Tf2N]

73[bmim][CF3CO2]

585[hmim][PF6]

450[bmim][PF6]

233[bmim][BF4]

43[emim][BF4]

Viscosity at 25°C, cpIonic Liquid


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• High thermal stability• Low viscosity compared to other ILs• High solubility for CO2 compared to other ILs• Low solubility for H2 compared to other ILs

Comparison of the available information on different classes of ionic liquids (ILs) showed that the Tf2N family

is suitable for application as separation medium in reforming and WGS reactions, because it has:


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0

2

4

6

8

10

12

14

16

0 0.2 0.4 0.6

mole fraction CO2

P, M

Pa

330 K

350 K

370 K

390 K

410 K

430 K

450 K

CO2 + 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)amid

CO2 + ionic liquid (T=350 K)

0

20

40

0 0.2 0.4 0.6 0.8

Mole Fraction CO2

P(M

Pa)

[bmim][Tf2N]

[bmim][PF6], Shariati et al. (2005)

[bmim][BF4], Kroon et al. (2005)


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The Dutch GCEP team

Left to right

Ir. Paul PexDr. Ruud van den BrinkDr. Wim HaijeIr. Daniel Jansen Ir. Jan Wilco Dijkstra Prof. Joop SchoonmanDr. Cor Peters

advanced membrane reactors in energy systems development

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