Catalytic Membrane Reactors by Developing New Nano …demcamer.org/pdfs_documentos/DEMCAMER Public Pr… · · 2016-07-13For the production of: • pure hydrogen • liquid hydrocarbons

01-02-2014 / Page 1

(Disclosure or reproduction without prior permission of DEMCAMER is prohibited).

Design and Manufacturing of Catalytic Membrane Reactors

by Developing New Nano-architectured Catalytic and

Selective Membrane Materials

This project is supported by the European Community’s Seventh Framework Programme Grant Agreement

Nº NMP3-LA-2011-262840

Duration: 4 years. Starting date: 01-July-2011 Contact: [email protected]

Then present document reflects only the author’s views and the Union is not liable for any use that may be made of the information contained therein.

mailto:[email protected]

01-02-2014 / Page 2


DEMCAMER’s Aim (I)

To develop innovative multifunctional Catalytic Membrane Reactors (CMR) Based on:

• new nano-architectured catalysts and • selective membranes materials

To improve the CMRs’: • performance • durability • cost effectiveness • sustainability:

• lower environmental impact • lower use of raw materials

Set up and validate pilot prototypes

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CMRs to be used for selected chemical processes: • Autothermal Reforming (ATR) • Fischer-Tropsch Synthesis (FTS) • Water Gas Shift (WGS) • Oxidative Coupling of Methane (OCM)

For the production of: • pure hydrogen • liquid hydrocarbons • ethylene

DEMCAMER’s Aim (II)

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DEMCAMER Partnership

This research is carried out by a multidisciplinary and complementary team consisting of 17 top level European organisations from 10 countries: 8 research institutes and universities working together with representative top industries in different sectors (from raw materials suppliers to chemical end-users).

University of Calabria

http://www.csic.es/

http://www.tue.nl/english/

01-02-2014 / Page 5


1. TECNALIA, Spain 2. VITO, Belgium 3. UNICAL, Italy 4. TU/e, The Netherlands 5. ICP-CSIC, Spain 6. FhG-IKTS, Germany 7. BIC, Russian Federation 8. INERIS, France 9. RKV, German 10. CERPOTECH, Norway 11. HYBRID, The Netherlands 12. HYGEAR, The Netherlands 13. ABNT, Spain 14. QUANTIS, Switzerland 15. HÖGANÄS, Sweden 16. TOTAL RC, Belgium 17. TOTAL EP, France

Consortium Composition



http://www.csic.es/

01-02-2014 / Page 6


Development of novel catalyst materials Development of innovative membranes Novel catalytic membrane reactors designed:

• on the basis of novel catalysts and membranes • using new reactor configurations • supported by simulation

Modelling and simulation at different levels: • materials (membranes and catalysts) • reactor prototypes • control system

Lab scale and prototype reactors testing and validation Life Cycle Analysis, industrial risk assessment study

Project Structure

01-02-2014 / Page 7


Partnership Synergies

01-02-2014 / Page 8


WP2. Industrial specifications [HYGEAR]

WP3. Catalysts development [CSIC] • Catalyst preparation • Catalyst characterisation • Activity test • Scale up

WP5. Lab scale reactors [TU/e] • Integration in CMRs • Testing of CMRs

WP6. Pilot prototype [HYGEAR] • Design of Pilot • Set up

WP7. Testing and Validation [ABNT] • FAT • Testing and validation

WP4. Membrane development [VITO]

• Material for membranes • Membranes support • Membranes development and

characterization

WP8. Modeling and Simulation [UNICAL] • Ab initio calculations • Transport in membranes • CMR simulations • Process simulations

• Pilot scale simulation

WP1

1. S

cien

tific

coor

dina

tion

[TU

/e]

WP1

0. D

isse

min

atio

n an

d Ex

ploi

tatio

n [U

NIC

AL]

WP1

. Man

agem

ent [

TECN

ALIA

]

WP9

. LCA

and

Saf

ety

issu

es [I

NER

IS]

Overview of the Work Structure

01-02-2014 / Page 9


New membrane materials and nano-architectured catalysts • improved properties • long durability • reduced cost

Better understanding of

• fundamental physicochemical mechanisms • relationship between structure/property/performance • manufacturing process of membranes and catalysts

Achieving radical improvements in membrane reactors’ • design • modelling • efficiency of configurations

Scientific and Technical Objectives (I)

01-02-2014 / Page 10


Scientific and Technical Objectives (II)

Validating reactor configurations • at semi-industrial prototype level • in all four selected chemical process (ATR, WGS, OCM, FTS) • for pure hydrogen, liquid hydrocarbons and ethylene production

Improving cost efficiency of reactors by

• increasing their performance • decreasing raw materials consumption • decreasing associated energy losses

Use of new raw materials (i.e. convert non-reactive raw materials)

Assessment of the four CMR developed processes’

• health and safety • environmental impact • a complete LCA of the developed technologies

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Development of catalytic materials Physicochemical characterisation Activity tests Scale-up and confirmation

Catalysts for ATR - WGS - OCM - FTS Reactions

01-02-2014 / Page 12


Development of novel materials and membranes for application in CMRs

MIEC membranes

Hollow fibres (H2 and O2 permeation)

Coatings (O2 permeation)

Metallic membranes (H2 permeation)

Zeolite membranes (H2 permeation and

water removal)

Membranes ATR - WGS - OCM - FTS Reactions

01-02-2014 / Page 13


Development of Materials for Novel Membranes

Perovskite powders for MIEC membranes Selection and manufacture of a wide range of feedstock powders for the

development of hollow fibres for O2 and H2 permeation Materials for inter-diffusion layers of metal based membranes Manufacture of Al2O3 and YSZ based powders for development of layers by

thermal spraying

before granulation after granulation

Optimisation of morphology by freeze granulation process

01-02-2014 / Page 14


Advantages: The membrane used as structure

directing agent can be readily removed at the end of the reaction, thus avoiding challenging purification procedures .

The method is simple, eco-friendly

and highly reproducible.

The method could be favourably extended to other microporous alumino-silicate of different topologies.

Nanocrystals having FAU-Y topology with uniform particles size distribution have been prepared in high yield through an organic-template-free hydrothermal synthesis by using a FAU membrane as structure directing agents.

Development of Materials for Zeolites

01-02-2014 / Page 15


Development of High-Quality Metallic Supports for MIEC and Metal-Based Membranes

Materials for metallic membrane supports • Selection of powder metal to meet reaction working temperature, e.g. stainless

steel in hydrogen permeation and nickel based material in MIEC application. • Selection of powder particle morphology (e.g. distribution, size and shape) to

generate required porosity and surface quality of metallic supports.

Metallic membrane supports • Porous tubes in different sizes.

Cross section of sintered tube

01-02-2014 / Page 16


Development of perovskite membranes by spinning and phase inversion methods

MIEC Membranes

A-site B-site O2- 2θ

Inte

nsity

a.u

.

Characterisation: XRD, SEM analyses and O2 permeation measurements

01-02-2014 / Page 17


Development of Pd-Ag supported membranes by direct PVD-magnetron sputtering or Electroless Plating techniques

Dense metal membranes for H2 separation

H2 permeance at 400 ºC: 1.75 x 10-6 mol m-2 s-1 Pa-1 H2/N2 ideal selectivity at 400 ºC: 9,000

Pd layer (4.0-4.2 µm thick) deposited by PVD on 200 nm pore size alumina tube

14.5 cm

PVD-MS equipment

Ceramic supported Pd-Ag membranes

01-02-2014 / Page 18


Improvement of FAU membrane layer by anchoring of the zeolite seeds onto support

Permeation tests: single and mixed gas (dry and humidified)

Structural characterisation: XRD and SEM analyses

0

1000

2000

3000

4000

4 10 16 22 28 34 40 46 52 58 64 70

2 theta

Inte

ns

ity

, a

.u.

Zeolite Membranes for H2 and Water Separation


01-02-2014 / Page 19


Selection of Catalytic Membranes Reactors components: • catalysts • membranes materials • supports • sealings

Integration of these elements into lab-scale reactors specifically

designed for ATR, WGS, OCM and FTS

Validation of the performance of lab-scale reactors Identification of best designs for pilot prototypes

Development of Lab-Scale CMRs

01-02-2014 / Page 20


Reactor Configurations - ATR

Reverse flow CMR concept for combined high-temperature O2 separation and autothermal reforming of methane


01-02-2014 / Page 21


Reactor Configurations - WGS

Micro-structured CMR concept

maximisation of membrane area complete process integration

unique mass and heat transfer capabilities

maximal energy and mass transfer efficiency

WGS reaction and hydrogen separation coupled in one single unit

CO + H2O ↔ CO2 + H2 ∆H𝟐𝟐𝟐

𝟎 = -41.09 kJ/mol



01-02-2014 / Page 22


CO,CO2,H2

H2

Furnace

GC 6890 Agilent

CO, CO2, H2, H2O(Retentate)

MFCH2COCO2

H2O

Permeate

PermeatePure H2 Retentate

Feed

Pd-Ag membraneCatalytic bed

Membrane reactor scheme

Experimental laboratory-scale plant

MR TR

Temperature, °C 350-400

Feed Pressure, bar 7- 9 7.5

Permeate Pressure, bar 1 -

H2O /CO feed molar ratio 1

GHSV (gas hourly space velocity) 8,000; 14,700; 36,700 h-1

Feed composition (dry), % CO:H2:CO2:N2 = 46:48:5:1

No sweep gas was used

WGS in a Fixed-Bed Membrane Reactor in


01-02-2014 / Page 23


Reactor Configurations - OCM

(modified from Caro et al., 2010)

CMR with packed-bed configuration

2CH4 + O2 → C2H4 + 2H2O ∆H298

0 = -141 kJ/mol CH4

optimising operating parameters (CH4/O2 feed ratio, T) to achieve enhanced CH4 conversion, best C2 selectivity and C2 product yield

01-02-2014 / Page 24


Shell

ReactionCompartment(Syngas Feeding)

Catalystparticles

Membranes for theselective H2O removal

Permeate Side:

H2O + Gas sweep

HC’s

HC’s

PermeateSide: H2O

PermeateSide: H2O

P1

P2

P1 > P2

ReactionCompartment

Membrane

Cross-section View: PBMR

PermeateSide: H2O

CatalystParticles

Shell


Catalystparticles


Permeate Side:

H2O + Gas sweep

HC’s

HC’s

PermeateSide: H2O

PermeateSide: H2O

P1

P2

P1 > P2

ReactionCompartment

Membrane


PermeateSide: H2O

CatalystParticles

Reactor Configurations - FTS

catalytic membrane milli-reactor in-situ water removal

packed bed membrane reactor distributed feeding

in-situ water removal

Shell

ReactionCompartment(CO Feeding)

Membranes for thedistributed feeding of H2

Catalystparticles

H2 Feeding

HC’s + H2O

P1 P2

P1 > P2

CatalystParticles

ReactionCompartment

Membrane


H2CO

Shell

ReactionCompartment(CO Feeding)

Membranes for thedistributed feeding of H2

Catalystparticles

H2 Feeding

HC’s + H2O

P1 P2

P1 > P2

CatalystParticles

ReactionCompartment

Membrane


H2CO

Shell


Catalystparticles


Permeate Side:

H2O + Gas sweep

PermeateSide: H2O

P1

CatalystLayer

ReactionChannel

Membrane

Cross-section View: CMM

PermeateSide: H2O

PermeateSide: H2O

P2

P1

P1 > P2

HC’s

HC’sShell


Catalystparticles


Permeate Side:

H2O + Gas sweep

PermeateSide: H2O

P1

CatalystLayer

ReactionChannel

Membrane

Cross-section View: CMM

PermeateSide: H2O

PermeateSide: H2O

P2

P1

P1 > P2

HC’s

HC’s

01-02-2014 / Page 25


Modelling and Simulation (I)

For membranes: Study of zeolite membranes properties by means of molecular modelling

and quantum chemical calculations: • Identification of structure-function relationships at molecular level • Identification of the optimal procedure for evaluating the selectivity • Identification selectivity of gases

Comparative analysis between the fundamental transport properties of • Pd and Pd-based alloys and • the corresponding properties of new (non-Pd) alloys formed from

different metals For catalysts: Search for the optimal catalyst’s structure for ATR, WGS, OCM, FTS by

correlation between their morphological and structural properties and their catalytic performance

01-02-2014 / Page 26


For ATR: Develop a reliable dynamic model in a reverse-flow membrane reactor For WGS: Develop a phenomenological model for fluidised-bed membrane micro-

reactors • Develop a reliable 2D model for membrane micro-reactors • Compare fluidised bed and packed-bed membrane micro-reactors • Analyse 1D or 2D dimensionless models for fixed-bed membrane reactor

For OCM: Develop a reliable 1D detailed model for the study of hollow fibre MIEC

membranes reactors with packed-bed configuration For FTS: 2D simulations of a fixed-bed catalytic membrane reactor

Modelling and Simulation (II)

01-02-2014 / Page 27


Evaluation of the membrane separation properties: Mathematical models describing the permeation in metal and zeolite

membranes Identification of elementary steps affecting the permeation through the

membrane and their influence on mass transport properties Processes: Design of new processes integrated with catalytic membrane reactors Analysis of the performance of the integrated processes as function of the

operating conditions assuring the best performance of the whole integrated process

Pilot scale: Modelling of the pilot scale reactors for ATR, WGS, OCM and FTS Definition and modelling of control strategies and control routines for the

pilot scale reactors

Modelling and Simulation (III)

01-02-2014 / Page 28


Porous support

Pd-based layer1

3

4

Layer 1

Layer n

Layer 1

Layer n

Por

ous

supp

ort

Pd-based layer

Feed Side

Permeate Side

Me

mb

ran

e l

ay

ers

Bulk Diffusion

Desorption

Bulk-to-Surface

Surface-to-Bulk

Adsorption

MulticomponentMass Transfer

Gaseous Film

Pd-

base

d la

yer

Mass transferin the pores

MulticomponentMass Transfer

Ma

ss

tra

ns

f er

me

ch

an

i sm

s

Gaseous Film

Porous support

2

Phys

ical

syst

em

Mat

hem

atic

al d

escr

iptio

n

Model based on a multicomponent approach

Modelling Example (I) Transport in Metal-Based Membranes


01-02-2014 / Page 29


Catalytic bed

Pd-Ag membrane

Retentate

PermeatePure H2

Feed

Pd-Ag MR Traditional

reactor

Temperature 300-450°C

Feed pressure 500, 1000;1500; 3000 kPa

Feed mixture composition

CO: H2O: CO2: H2: N2 =

31.25:31.3:25.5:33:1, % molar H2O/CO feed molar ratio 1

GHSV 10000 - 40000 h-1

0

0.5

1

CO C

onve

rsio

n, -

300 400 500Temperature, °C

TR

1500

10000 h-1

Modelling Example (II) WGS – Fixed-Bed Membrane Reactor


01-02-2014 / Page 30


NATURAL

GAS

Steam Methane

Reforming

H2 (high purity)

CO2

WGS MR

H2 (high purity)

H2 purification

WGS HT

Traditional Process

H2

(high purity)

CO2

CO2 separation

CO2 separation

H2 purification

WGS LT

Membrane Integrated Process

Modelling Example (III) WGS Process Simulation


01-02-2014 / Page 31


water

NG

Permeate (H2 highly pure)

RE

FOR

MIN

G

Retentate stream

WGS Membrane Reactor Integration

Alternative downstream post-treatments

H2

CO2

separation H2

purif

icat

ion

CO2 compression and storage

CO2 separation

WGS MR H

2 pu

rific

atio

n

H2 H2

WGS MR

Modelling Example (III) cont’d


01-02-2014 / Page 32


Modelling and Simulation Example (IV) Study of zeolite properties for membranes by means of molecular modelling

(quantum chemical approach) Identification of the optimal ab-initio quantum procedure for evaluating the

selectivity

Quantum Mechanics Approach: Embedded clusters (K. Walton et al., 2006)

DHads (T, gas) to be used in the ab-initio quantum procedure

CO molecule adsorbed on isolated Ca2+cation

CO molecule adsorbed on Ca2+cation embedded in LTA 6-ring

LTA supercage with 48 embedded in sites II Ca2+cation

CO

01-02-2014 / Page 33


Modelling and Simulation (V)

Comparative Study of the Hydrogen Trapping in non-Pd alloys Relationship between alloy atom composition and hydrogen stability and diffusivity

Computational Analyse H2 trapping process in metal alloys

Evaluation/knowledge fundamental quantities

Input for periodic calculations

Metal Alloy Screening by ASD

Ato

mic

Sca

le D

escr

ipto

r (A

SD)

01-02-2014 / Page 34


Design and setup of the pilot scale catalytic membrane reactors

Pilot reactors for ATR, WGS, OCM and FTS processes Depending on the working pressure all reactors will be designed and

manufactured according the “Pressure Equipment Directive” of the EC (97/23/EEC)

Overall system controls for the different reactor types will be designed and constructed to ensure automatic operation of the systems and safety aspects and control strategies developed according to Pilot scale modelling

All system components will be mounted into an enclosure and will undergo a Factory Acceptance Test (FAT) before being set into operation for validation and testing.

Pilot Scale Prototypes

01-02-2014 / Page 35


Testing and validation of the pilot scale prototype reactors

For testing and validating of the pilots, corresponding test plans and protocols will be defined including parameters and/or values that have to be derived from the tests, such as system efficiency, etc.

Results will be compared to the requirements and specifications

Test results will be used in Modelling and Simulation to validate and improve the pilot scale models and the system control strategies, as well as for the LCA and the accidental industrial risk assessment

Pilot Prototypes Testing and Validation

01-02-2014 / Page 36


Life Cycle Assessment and Safety Issues

Assessment of socio-economic sustainability of the proposed technologies from an environmental and safety perspective.

Environmental Life Cycle Assessment analysis of the CMR process

Identification and evaluation of key safety parameters and risk analysis

Proposal of recommendations for the safe operation of the CMR technology

Socio-economic analysis to evaluate the sustainability and feasibility of the CMR technology (process performance, environmental and safety constraints) compared to currently available technologies

Socio-Economic Analysis

Safety Constraints

Process Performance Constraints

Environmental

Constraints

01-02-2014 / Page 37


Environmental Life Cycle Assessment

• DEMCAMER will perform a robust environmental Life Cycle Assessment (LCA) of the new technologies to be developed (CMR) compared with the reference technologies (baseline)

• Within DEMCAMER, the LCA focuses on the following environmental impact categories over the entire life cycle of the processes:

− Greenhouse gas (GHG) emissions (climate change) − Non-renewable primary energy use − Direct and indirect impacts on human health − Direct and indirect impact on ecosystems − Water use (incl. water impact assessment)

Objectives of the Life Cycle Assessment

01-02-2014 / Page 38


Environmental Life Cycle Assessment

Reference technology (baseline) CMR technology

compared with

Objectives of the Life Cycle Assessment – Example of ATR-CMR

01-02-2014 / Page 39


Thank you for your attention

Documents

Catalytic Membrane Reactors by Developing New Nano …demcamer.org/pdfs_documentos/DEMCAMER Public Pr… · · 2016-07-13For the production of: • pure hydrogen • liquid hydrocarbons