Advanced m-CHP systems - · PDF file14/10/2015 / Page 3 (Disclosure or reproduction without prior permission of FERRET, FluidCELL and ReforCELL is prohibited). PROJECT TARGETS AND

14/10/2015 / Page 1 (Disclosure or reproduction without prior permission of FERRET, FluidCELL and ReforCELL is prohibited).

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Advanced Multi-Fuel Reformer for Fuel CELL

CHP Systems ( ReforCELL – 278997)

A Flexible natural gas membrane Reformer

for m-CHP applications (FERRET – 621181)

Advanced m-CHP fuel CELL system based on

a novel bio-ethanol Fluidized bed membrane

reformer (FluidCELL - 621196)


José Luis Viviente

Fundación Tecnalia Research & Innovation

www.reforcell.eu; www.fluidcell.eu

Fausto Gallucci

Eindhoven University of Technology

www.ferret-h2.eu

Advanced m-CHP systems

http://www.reforcell.eu/

http://www.fluidcell.eu/

http://www.ferret-h2.eu/




NG Flexibility vs.

NG composition Ethanol

PROJECT TARGETS AND ACHIEVEMENTS:

The concept


PROJECT TARGETS AND ACHIEVEMENTS

Programme objective/target

Project objective/target

Project achievements to-

date

Expected final achievement

MAIP

Micro-CHP (residential), natural

gas based 2020 target: 5,000 € per system (1kWe +

household heat).

5,000 € (1kWe + house heat) by

2020

Cost could be achieved for mass production. m-CHP

system will be assembled beginning

November.

Dynamic response of power and heat Feeding the FC with another H2 source. m-CHP system validated

Overall efficiency > 80% for CHP units

Overall efficiency > 90%

90 % can be achieved if the appropriate

heat exchanger and insulation is adopted

Overall efficiency > 90%

Lower emissions and use of multiple fuels

Different natural gas

Reduced CO2 emissions .

Bio-ethanol as fuel

NA 100%


PROJECT TARGETS AND ACHIEVEMENTS

Programme objective/target

Project objective/target

Project achievements to-

date

Expected final achievement

AIP

Viable mass production

Mass production technologies

Mass production technologies

100%

CHP life time (years) > 10

> 10 but not tested in the project

N/A. Test <10 years 400 h test 2000 h test

Electrical efficiency (%) >42%

> 42% 42 % net electric efficiency is feasible

100%

Recyclability LCA and safety study Preliminary LCA 100%

Proof-of-Concept of CHP in lab

TRL 4 – technology validated in lab

60% 100%

Durability of several hundreds of continuous

operating hours

1000h of operation at nominal power

output

50% 100%


Catalyst screening in steam methane reforming (SMR) revealed a

catalyst that meets the requirements set by ReforCELL (i.e. 600 ᵒC)

The catalyst is comprised of Ru supported on mixed Zr/Ce-oxide.

The catalyst is also active at significant lower temperature (500

ᵒC) than originally anticipated.

The catalyst synthesis has been scaled up to afford kg quantities.

0 5 10 15 20 25 30

0

10

20

30

40

50

60

70

80

90

Weig

ht ch

ange [m

g]

Time (h)

Steam [g/h]

RhZrO2 sample [mg]

NiAl2O

3 sample [mg]

Steam [g/h]

Carbon formation on commercial and new catalyst Experimental results and modeling


Catalyst development ReforCELL


Catalyst surpasses activity and stability targets for FERRET

Displays activity across a wide range of natural gas compositions

Stable to fluidization testing without loss of particle size or

sphericity

Scalable preparation methods

Particle size distribution of

catalysts before sieving, after

sieving and after cold and hot

fluidization in air.


Catalyst development FERRET


Preparation: Sequential impregnation of CeO2, Ni and Pt followed

by drying overnight at 120oC and calcination at 600oC for 3h

Final formulation: 3wt%Pt-10wt%Ni/CeO2/SiO2

Mechanical support: SiO2 assures proper

resistance during fluidization

Catalytic support: CeO2 promotes dissociation of

H2O and C2H5OH molecules and prevents coking

Non-noble metal: Nickel favors C-C bond break

Noble metal: Platinum enhances WGS activity


Catalyst development FluidCELL



Membrane development

Pd-based membranes by direct deposition of thin dense metal

layers (< 5 µm) onto ceramic and metallic tubular supports by

simultaneous ELP or combined ELP & PVD.

Pd-based tubular membranes on metallic supports by the 2-step

coating method (PVD + wrapping).

H2 permeance and H2/N2 ideal selectivity above the project targets

(and DoE targets).

Work is ongoing to increase the stability at high temperature (600 -

650 ºC)

0

50000

100000

150000

200000

250000

300000

350000

0.0E+00

4.0E-07

8.0E-07

1.2E-06

1.6E-06

2.0E-06

2.4E-06

2.8E-06

0 100 200 300 400 500 600 700 800

Ide

al

se

lectivity H

2/N

2

Pe

rme

an

ce

H2

(mo

l/s/m

2/P

a)

Time (h)

500 C 525 C 550 C 575 C 600 C

SH2/N2= 2650

Membrane M17-E94.

Long-term stability test Metallic supported membrane M14.

Long-term stability test over time at 400 ºC

http://www.google.es/url?sa=i&source=images&cd=&cad=rja&docid=1-nWmnf3UOQnYM&tbnid=efa_r5o_WGIFBM:&ved=0CAgQjRwwAA&url=http://orbitshipping.in/Satelite.html&ei=8K97UoPUNIem0AXysoCgCA&psig=AFQjCNH7FGbpHlqaI2yoEk7eF5RjZvdE_Q&ust=1383924080896708


Pd-Ag-Au membranes by ELP (Au layer

onto a Pd-Ag membrane + thermal

treatment

H2 permeance=1.6 x 10-6 mol m-2 s-1 Pa-1;

Ideal H2/N2 selectivity= ~1600

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

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: ~4 µm.


Membrane development




Membrane development: Ongoing/next activities

Pd pore filled membranes for high (>500 ºC)

and moderate conditions (< 500 ºC).

Using thicker ceramic porous support (10/4

mm instead of 10/7 mm) for improving

mechanical stability.

Optimising the process for developing metallic

supported membranes.

Pd-Ag-Au and Pd-Ag-Ru based membranes by

ELP and/or combined ELP & PVD.

PVD will be used for adding a 3rd metal (i.e.

Au, Ru,..) to Pd-Ag membranes developed by

ELP.

+30 mm



System operated for 2 weeks continuously

Good catalyst stability but membranes to be improved


Lab-scale testing - ReforCELL Design, construction and testing of the lab-

scale reactors specifically designed for ATR.

Integration strategies for the different CMR

components: catalysts, membranes and

supports (i.e. sealing)

Modeling of ATR reactor types and Validation

of the lab scale reactor concepts


Methane conversion at different pressures (550°C; SMR: S/C=3; ATR: O/C=0.25)

Catalyst stable under fluidized conditions in MR

MR system has higher conversions than equilibrium for

conventional systems


Lab-scale testing - ReforCELL


72,00

76,00

80,00

84,00

0 0,5 1 1,5 2 2,5 3 3,5 4

Xco

(%

)

Reactor pressure (bar)

Xco

Xeq

Xco,mem

Temperature: 400 °C, CO (9.2%), H2O (19%), CH4 (4%),

H2 (30%), N2 balance, U/Umf:1.67-5, Pperm: 30 mbar

0,00

1,00

2,00

3,00

4,00

5,00

6,00

7,00

0 0,5 1 1,5 2 2,5 3

pp

m


CO (ppm)



0,00

0,10

0,20

0,30

0,40

0,50

0,60

0 0,5 1 1,5 2 2,5 3

HR

F


HRF



0,00

5,00

10,00

15,00

20,00

25,00

30,00

35,00

40,00

45,00

50,00

0 0,5 1 1,5 2 2,5 3

pp

m


CO2 (ppm)



Preliminary results with 5 membranes – up to 60%

recovery and < 10 ppm CO in H2


Lab-scale testing - FluidCELL



Objective: Design and set up of the pilot scale ATR CM reactor.

Design novel ATR reformer according

PED 97/23 EC

5 Nm3/h hydrogen production

Fluidized bed

Partial loads down to 30%

Maximum temperature 600 ⁰C

Nominal pressure 8 bara

Vacuum on permeate side


Design and manufacturing of novel ATR reformer


Future work: ATR testing. Feedstock flexibility. Ethanol

Testing under reactive conditions

Modulation at partial loads.

Tuning of controls

Feedback to other projects using similar technology for different

feedstock

FERRET: Flexibility to varying NG compositions across EU

FluidCELL: Ethanol membrane reformer


Design and manufacturing of novel ATR reformer



Fuel cell stack

240 260 280 300 320 340 360 380 4000

50

100

Temps (h)

I (A

)

240 260 280 300 320 340 360 380 400

4

4.5

5

5.5

6

6.5

Temps (h)

U (

V)

240 260 280 300 320 340 360 380 400

61

63

65

67

69

71

73

75

Temps (h)

T (

°C)

240 260 280 300 320 340 360 380 4001

1.2

1.4

1.6

Temps (h)

P (

ba

r)

240 260 280 300 320 340 360 380 40020

40

60

80

Temps (h)

RH

(%

)

240 260 280 300 320 340 360 380 4000

1000

2000

3000

Temps (h)

Q (

Nl/h

)

Température

Tension

Courant

Débit anode

Débit cathode

Pression anode

Pression cathode

HR anode

HR cathode

Stack prototype (85cell) designed, made

and validated for system integration

Load cycles (based on 1 day use) H2 + 10ppm CO or 50ppm+AB

Effect of Air bleeding at 50ppm (after cycles)

70C - P fuel = 1,2 bars – Pair=1,3bars – RH50%

Reversibility under

H2 ok after cycles

50ppm+AB

10ppm

Validation on short stacks (8 cells)

Note: short validation with High

CO contents & AB (up to 300ppm)

Performance of 85 cells

stack = 8 cells stack

Final test after cycles:

OK!


Integration and validation of the CHP system


Fuel cell CHP system optimisation

In ReforCELL, the plant lay-out and operating conditions were optimized

to achieve high efficiency (>40%), while limiting the membrane surface

area (<0.3 m2); Reference system efficiency 32%;

Different options were evaluated both for the membrane reactor

permeate side and heat recovery arrangements;

PEM

Fuel Cell

Cathode

Anode

P-1

H2Oreaction

air+H2Oreaction

CMPNG

Retentate

HX-8

(Recov)

Exhaust

waterrec.

H2

H2+H2Osweep

HX-7

HX-6

P-3

Cooling circuit

Aircath

CMPair

AirATR

Sep

H2Osweep

Sep

P-2

H2Osweep

ATR-MR

(600°C)

Sep

Burner

HX-4

HX-2

Airbrn

HX-0

HX-1 HX-3

HX-5

HX-5

Qdiss

Qdiss

Results units Sweep

VP

S/Ca - 2.5 3

Pressure reaction side bar 8 8

Pressure permeate side bar 1.2 0.3

NG power input [LHV base] kW 12.50 13.05

Net AC power output kW 5.00 5.00

Fuel Cell AC power output kW 6.31 6.63

Net electric efficiency %LHV 40.02 38.32

Net thermal efficiency %LHV 51.97 51.86

Total efficiency %LHV 91.99 90.18

Total membrane area m2 0.29 0.19




In FERRET, the lay-out was defined according to ReforCELL achievements

and the system performances with different natural gas compositions

was assessed (simulation). In addition, electric and thermal efficiency at

partial load were also determined.

41.0%

41.2%

41.4%

41.6%

41.8%

42.0%

3.40

3.41

3.42

3.43

3.44

3.45

UK8 bar

IT8 bar

NL8 bar

ES8 bar

Net

El.

Eff

. (%

)

H2

pe

rm (

Nm

3/h

)

H2 perm Net El. eff.

52

53

54

55

56

57

38

39

40

41

42

43

30 40 50 60 70 80 90 100

Th. E

ffic

ien

cy (

%)

El. E

ffic

ien

cy (

%)

Load (%)

Fuel cell CHP system optimisation




Regarding the Life Cycle Assessment (LCA) activities, data specific to

ReforCELL m-CHP system and for alternative systems have been

collected from project partners and in literature

The environmental impacts of the ReforCELL system have been

calculated, showing the interest of ReforCELL in comparison with

other fuel cell m-CHP systems and with conventional electricity and

heat. ReforCELL is however more impacting than wind power and solar

thermal (i.e., green available technology)

The LCA identified the efficiency, the dimensioning and rare metals

use (in fuel cell and fuel processor catalyst) as key parameters for the

environmental impacts


LCA and safety assessment


Next steps and synergies with other projects


LCA and safety assessment: next steps - synergies

Assess the influence of dimensioning on the environmental

impacts of fuel cell m-CHP systems

• Through detailed LCA assessment for ReforCELL (by end 2015)

• Through FluidCELL project

Explore other input fuels (e.g., biofuels)


Include more scenarios on fuel cell, fuel processor and balance-of-

plant components and use LCA as a decision support tool



RISKS AND MITIGATION

Failure of the membrane reactor prototype.

Mitigation: - Dynamic response of power and heat production assessed

feeding the Fuel Cell with another H2 source. So the m-CHP

new design system will be validated.

- Improving the FAT procedure for the prototype.

Failure of the membrane when integrating them in the prototype.

Mitigation: - Using membranes with higher mechanical stability such as:

i) Thicker ceramic supported membranes (i.e. 10/4 instead of 10/7

mm) or ii) Metallic supported membranes.

- Sealing more stable at high temperature (already OK for 2 weeks).

- Improving the handling procedure for the integration of the

membranes.

Dead-end Porous part Open-end

Long term stability of the membranes

Mitigation: - Improving membrane stability by:

i) adding Ru and/or Au in the selective layer,

ii) better interdiffusion layer and lower thermal expansion mismatch

iii) thicker ceramic supported membranes.


HORIZONTAL ACTIVITIES

Technology oriented workshop has been organised with other FCH

JU/ EC funded projects that share similar technological challenges:

Joint workshop “Scale-up of Pd Membrane Technology From

Fundamental Understanding to Pilot Demonstration” with other

FCH JU/EU projects (DEMCAMER, CARENA, ReforCELL and

CoMETHy) held in November 20-21, 2014 at ECN, Westerduinweg

3, 1755 LE Petten,The Netherlands

Safety, Regulations, Codes and Standards

Safety issues addressed in WP8 (LCA and safety issues) for both the

CMR and the complete system. Identification and evaluation of safety

parameters (i.e. CMR: prevent thermal runaways or hot spots)

The development of the final m-CHP system could provide a feedback

on regulation, codes and standards


DISSEMINATION ACTIVITIES

Dissemination & public awareness

Public website (www.reforcell.eu; www.ferret-h2.eu;

www.fluidcell.eu

6 monthly newsletter & public project presentation

Towards national and international organisation related to the R&D

field.

Participation in international and national conferences and

workshops (i.e. 22 presentations, 5 posters).

6 articles, 3 book chapters.

Final dissemination







EXPLOITATION PLAN/EXPECTED IMPACT

The R&D is opening the way to novel and cheaper m-CHP systems for

grid and decentralized off-grid applications.

Flexibility to use different natural gas qualities and bioethanol grades

as fuels.

Reduced CO2 emissions compared to conventional reformers.

Reduced anthropogenic CO2 emissions compared to conventional

fossil fuels.

Industrial partners in the value chain are members of the consortia.

Ownership of the different components are clearly identified.

Development are considering mass production technologies as well as

standard components when possible.


Thank you for your attention

José Luis Viviente

Fundación Tecnalia Research & Innovation

www.reforcell.eu; www.fluidcell.eu

Fausto Gallucci

Eindhoven University of Technology

www.ferret-h2.eu

Contacts:

Advanced m-CHP systems






Documents

Advanced m-CHP systems - · PDF file14/10/2015 / Page 3 (Disclosure or reproduction without prior permission of FERRET, FluidCELL and ReforCELL is prohibited). PROJECT TARGETS AND