A Flexible natural gas membrane Reformer for m- … Flexible natural gas membrane ... Displays activity across a ... Safeguarding stability of fragile membranes during transport Pilot

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A Flexible natural gas

membrane Reformer for m-

CHP applications

FERRET

This project is supported by the European Union’s Seventh Framework Programme (FP7/2007-2013) for the Fuel Cells and Hydrogen Joint Technology Initiative under grant agreement nº 621181

Duration: 3 years. Starting date: 01-Apr-2014

Contact: [email protected]

The present publication reflects only the author’s views and the FCH JU and the Union

are not liable for any use that may be made of the information contained therein.

mailto:[email protected]


Summary

FERRET aims at developing a high efficient heat and power cogeneration

system based on:

i) design, construction and testing of a flexible advanced reformer for pure

hydrogen production from a broad range of natural gas with optimization

of all the components of the reformer (catalyst, membranes, heat

management etc.) and

ii) the design and optimization of all the BoP for the integration of the

novel reforming technology in a CHP system.

The main idea of FERRET is to develop a novel more efficient and cheaper

multi-fuel membrane reformer for pure hydrogen production in order to

intensify the process of hydrogen production through the integration of

reforming and purification in one single unit


Partnership

Multidisciplinary and complementary team: 6 top level European organisations from

4 countries: 3 Research Institutes and Universities and 3 top industries in different

sectors (from hydrogen production to catalyst developments to boilers etc.).

TU/e, Netherlands

TECNALIA, Spain

POLIMI, Italy

ICI, Italy

HyGear, Netherlands

Johnson Matthey (UK)


Scale-up of membranes and development of new pore-filled membranes

more resistant to fluidized bed membrane reactor configuration and using

less amount of Pd per m3/h of hydrogen production

Reduction of fuel processor costs

Development of methods for recycling and repairing of Pd-based membranes

Improvement of catalyst for reforming of different natural gas compositions

Scale up the catalyst production for fluidized bed applications

Improvement of a novel fluidized bed membrane reforming reactor of

different natural gas compositions

Improvement of a novel fluidized bed membrane reforming reactor for long-

term performance.

Protection of Fuel cell stack (e.g. Cr release), CO poisoning

Integration of the novel reforming in a CHP system

Optimization of the BoP for the novel reforming CHP system

Simulation and optimization of the reformer integration with the entire

system

Project objectives


Work structure


Partnership synergies


Catalyst development

Develop an autothermal reforming catalyst to convert a mixture of natural

gas, steam and air into syngas (hydrogen, carbon monoxide, carbon dioxide,

nitrogen).

The catalyst needs to be mechanically durable and operate as a fluidized

bed inside a membrane reactor.

The catalyst needs to maintain activity under membrane reactor

operating conditions.

Scale up of catalyst production

Objectives:



Catalyst development focused transition metal oxide supports

Chosen for mechanical and thermal stability

Catalysts made by doping PGM on to support materials

Additional metal dopants strengthened activity and long term stability of

the catalyst

Catalyst Testing:



Catalyst surpasses activity and stability targets for the FERRET project

Displays activity across a wide range of natural gas compositions

Stable to fluidization testing without loss of particle size or sphericity

Scalable preparation methods

Status:


Particle size distribution of catalysts before sieving, after sieving and after cold and hot fluidization in air.



Membranes development

Development of Pd based tubular membranes, for application in

natural gas autothermal reforming catalytic membrane reactors

Improved flux and selectivity

Temperature 600 ºC

Improved sulphur resistance

Resistant to fluidization regime

Process scaling up

Objectives:


Sample Pd-Ag thickness (µm)

N2 permeance x10-9 (mol m-2 s-1 Pa-1) at 25 ºC

ZrO2 3 nm ---- 24,600 ±434

PVD on ZrO2 3 nm

~ 0.5 15,143 ±1,292

Pd-Ag membranes by direct

PVD deposition

The Pd-Ag film is not dense on porous supports.

It is not possible to prepare suitable Pd-Ag membranes by one step direct

PVD deposition onto porous supports.

Suitable membranes could be obtained by a double process: PVD + ELP or

ELP+PVD.

PVD could be used for increasing the Ag amount as well as for adding a 3rd

metal (i.e. Au, Ru,..) to Pd-Ag membranes developed by ELP.

Al2O3 200 nm


Thickness profile at various target levels

+30 mm

PVD-MS at Tecnalia could coat up to 78 supports (Ø10 mm) simultaneously.

Ru and Au will be deposited on Pd-Ag membranes by PVD-MS

Membranes by direct PVD deposition:


Au layer was deposited by ELP on a Pd-Ag membrane

The Pd76-Ag12-Au10 was formed by thermal treatment

H2, N2 permeation test (550ºC, ~1 bar)

H2 permeation increases until a plateau is reached at around 500 min

H2 permeance=1.6 x 10-6 mol m-2 s-1 Pa-1; Ideal H2/N2 selectivity= ~1600

Pd-Ag-Au membranes by ELP


Pd-Ag membranes supported onto ZrO2 tubular porous supports (Ø10 mm)

prepared by simultaneous Pd & Ag ELP deposition.

Length of the Pd-Ag membrane 22-23 cm ( 50% longer than planned)

Thickness of the selective layer: 3-4 µm

21 Pd-Ag membranes have been already delivered.

Pd-Ag membranes for the prototype


Pd

Al

Al

Thin Pd film membrane

Pore-fill type Pd membrane

Thin Pd film membrane

Pore-fill type Pd membrane

Advantages of pore filled over conventional membranes

- Less Pd is used (a fraction of conventional)

- Protection under fluidization regime

Composite nano porous membranes Packed with Palladium panoparticles

(pore filled membranes)

Pd pore filled membrane


Membrane preparation Long term permeation test

Al2O3 (100 nm)

PF-A45

Seedings 60YSZ/40γ-Al2O3 + + Platings + + 60YSZ/40γ-Al2O3

1st coating Protective layer

Selectivity and H2 permeation still low

Thicker nanoporous layer are being prepared to increase permeation properties

Pd pore filled membrane


Selection of ATR-CMR components:

catalysts, membranes and supports,

and sealing based.

Integration of these elements in lab

scale reactors specifically designed for

ATR.

Validation of the lab scale reactors

performances and identification of the

best design for prototype pilot.

Lab scale reformer

Objectives:


Methane conversion at different pressures of experiment carried out at 550°C and S/C=3. For ATR O/C=0.25

Lab scale reformer


Objectives:

Design the pilot scale

catalytic membrane

reactor (CMR)

Construct and assemble

the pilot scale catalytic

membrane reactor

including controls

Perform functionality tests

before integration into

Fuel Cell CHP-system

Pilot scale catalytic membrane

reformer


Specifications:

Maximum H2 output 5 Nm3/h

Partial loads 30 % (1.5 Nm3/h)

Sweep gas (steam)

Design operating temperature up to 600 ºC

7 bar

Permeate ~ 200 mbarg

Hydrogen recovery up to 90 %


reformer


System assembly:

Portable skid; reduced footprint

Safeguarding stability of fragile membranes during transport


reformer

Reactor

Control

cabinet

Steam

generators

Flow

controllers

DeS

Methanator

Pumps


Test results:

Tests at 550 °C

• Steam-to-Carbon

• Feed flow


reformer


Test results:

Tests at 550 °C

• Sweep flow


reformer


Test results:

NG specifications from different sources


reformer

NG type

Species Unit NL UK IT ES

CH4 %mol 81.23 92.07 99.581 81.57

C2H6 %mol 2.85 3.41 0.056 13.38

C3H8 %mol 0.37 0.76 0.021 3.67

n-C4H10 %mol 0.08 0.18 0.002 0.40

i-C4H10 %mol 0.06 0.14 0.006 0.29

n-C5H12 %mol 0.02 0.05 0 0

i-C5H12 %mol 0.02 0.06 0.002 0

C6+ %mol 0.08 0.09 0.007 0

CO2 %mol 0.89 0.87 0.029 0

N2 %mol 14.4 2.37 0.296 0.69

LHV MJ/kg 38.0 46.7 49.7 48.6

LHV MJ/mol 0.708 0.819 0.801 0.939

H2 potential mol H2/mol NG 3.52 4.07 3.99 4.66

x in CxHy - 0.89 1.04 1.00 1.22

Wobbe index MJ/Nm3 43.6 52.0 53.1 56.6


Test results:

Stable operation with four NG compositions tested

Composition with high content of C3H8 showed lower conversion


reformer


Integration & Validation in

CHP-System

Definition of fuel cell CHP-model based on existing fuel cell CHP-system

Integrating the FERRET reformer into existing CHP-system

Evaluation of the FERRET CHP-system feeding different natural gas compositions

Compare performance of the FERRET CHP-system with existing CHP-system

Perform techno-economic analysis of the FERRET CHP-system



CHP-System

Activities:

Definition of the reference case lay-out and assessment of the

performances.

Survey of different NG composition around Europe.

Investigation on different lay-out and operating conditions for the FERRET

system.

Investigation on layout flexibility under different NG compositions.



CHP-System

Among the 37 different NG compositions available, 4 cases were selected

as reference for the project, representing the entire European situation.

A m-CHP system model was developed and validated using experimental

results from tests performed. The results from this analysis will be used as

reference case within the project.

The performance of FERRET unit is compared to this reference system:

28% for the net electric efficiency and 86% for the total efficiency of the

CHP system.

The layout of FERRET fuel cell CHP-system was defined. A good

compromise between efficiency and membrane area occurs at 8 bar and

873 K for the sweep gas case with a net electric and total respectively

higher than 41 % and 97%.

Influence of the four NG qualities on the performances of FERRET unit was

investigated.

Results:



CHP-System Results:

In general terms, the system flexibility is demonstrated by the limited efficiency

variation with the load and under different NG compositions

The net electric efficiency of the system increases s up to 70% of the rated load when

it starts to drop as consequence of the polarization curve of the PEM fuel cell.

The thermal efficiency reduces in the first part because of the higher electric efficiency



CHP-System Results:

0

500

1000

1500

2000

2500

3000

NL UK IT ES

Mic

ro-C

HP

targ

et c

ost

(€/k

W)

2.5

3.0

3.5

4.0

4.5

5.0

20

23

26

29

32

35

NL UK IT ES

Eq. h

ou

rs (

·10

3h

)

PES

(%

)

Primary Energy Savings Equivalent hours

The Ferret solution was applied to the different European residential loads

as well as economic boundaries.

The resulting yearly energy balance reveals that the PES is higher than 10%

in most of the cases;

The adoption of the micro-CHP system can reduce the annual operating

cost of around 1500 €.

The target micro-CHP specific cost can be around 2000 €/kW which is not

the current cost of the system but it can be achieved when the system is

industrialized and available in hundreds of thousands of units.


A Flexible natural gas

membrane Reformer for m-

CHP applications

FERRET

Thank you for your attention

Contact: [email protected]

Documents

A Flexible natural gas membrane Reformer for m- … Flexible natural gas membrane ... Displays activity across a ... Safeguarding stability of fragile membranes during transport Pilot