Enhancement in biomass gasification: tar-reduction and sorption … · 2018-03-15 · biomas-to-syngas conversion as well as the reduction of pollutant efficiency • The use of advanced

Enhancement in biomass gasification: tar-reduction and sorption enhanced reforming

D. Borello

Dipartimento Ingegneria Meccanica e AerospazialeSapienza Università di Roma

Domenico Borello, Ph.D.

SEA-Group at DIMA: who’s who

Professors (5)Franco Rispoli

Alessandro Corsini (Associate Professor, ASN-PO)Domenico Borello (RTD-B, ASN-PA)Luca Cedola, (past RTD-A), Andrea Micangeli (past RTD-A under evaluation as ASN-PA)

Research Assistant & PostDoc (9)Giovanni Delibra (ASN-PA),Paolo Venturini (ASN-PA),Katiuscia Cipri, Eileen Tortora, Andrea Marchegiani, Alessandro Tallini, Alessio Castorrini,

Sara Feudo, David Volponi

Ph.D. Candidates (2)Tommaso Bonanni, Fabrizio Bonacina

Ph.D. students (7)Francesca Lucchetta, Giuliano Agati, Lorenzo Tieghi, Gino Angelini,Arash Aghaalikhani, Riccardo Del Citto, Gabriele Gagliardi

ACADEMIC COLLABORATIONS

K. Hanjalic

J. Sesterhenn

J. VadY. Bazilevs

T. Tezduyar

K. Takizawa

J. Van der Spuy

R. Saavedra

J. Schmid

RELEVANT INDUSTRIAL COLLABORATIONS


Lab Activities at DIMA of SEA-Group

• Biomass Gasification: TAR reduction, SER and bio-assisted phyto-remediation - with

DICMA Sapienza, RESET, ISPRA, CNR, CISA, TU Wien, Universidad de Piura and

ENEA

• Direct Methanol Fuel Cells: advanced configurations – with CNR MM and

Fincantieri

• Lithium Batteries: Management &Verification - with MM and Fincantieri

• Development of CC4E (Clean Canvas 4 Environment) process – with Regione Lazio

• Biofuels in Internal Combustion Engines – with CURSA and Power Clean

• Pulse tube Stirling Engine: Molecular Freezing -to promote

• Coal Gasification, Steel and Cement industries: CCS techniques – with ENEA

• Design of Wave Energy Converter - with ENEA, OWEMES and MATTM


Why research in biomass gasification?

BIOMASSSustainable resource,

Renewable,CO2 neutral

GASIFICATIONThermochemical process,

production of fuel gas

SYNGASUseful to feed FuelCells, Turbines, ICE

Main issues: POLLUTANTS in syngas (particulate, TAR) GHG emissions (CO2, …)

CO2 CAPTURE

GAS CONDITIONING

• Need to increase the efficiency of the gasification process• Reduce pollution• Explore the potential of different feedstocks

Approaches (Experiments)

Catalytic TAR Steam Reforming

Tar removalAdditional fuel gas

Nickel BasedCatalysts

Very efficient and economic BUT Carbondeposition problems

Mayenite(Ca12Al14O33)

Good oxydating propertiesthanks to free oxygens in the structure


Sorption EnhancedReforming

Use of Calcium compoundsNegative CO2 process

b)

Approaches (Models)

Use of modelling software for prediction of plant performanceModelling of non-equilibriumconditions

ChemCadASPEN+, TRNSYS,UDFs

Use of in-house FEM-CFD for prediction of biomass combustionas well as soot tracking

Very efficient BUTcomputationallyexpensive


Outline

• Bench Scale Apparatus

•Tar Reduction

• Characterization of Ni/Mayenite catalyst (XRD, SEM,

BET, XRF)

• TAR and CH4 steam reforming

• Catalyst Regeneration (TPO)

• Catalyst performance after regeneration

• Sorption Enhanced Reforming

• Process description

•New developments: Phyto-remediation

• Partnerships&Publications Domenico Borello, Ph.D.

Bench scale apparatus

• Biomass used: hazelnut shells• C = 51.3 % d.a.f. H = 6.1 % d.a.f.O = 42.6 % d.a.f.

• Steam + air gasification• T = 800 - 820 °C• Steam to Biomass = 0.5• Equivalent Ratio = 0.3


• Ca(CO3) + Al2O3mechanical mix stoichiometric ratio 12:7

• Calcination at 900°C for 7 h

• Sieving between 200 and 700 microns

Synthesis of Ni/Mayenite

• Wet impregnation with Ni(NO3)2 to deposit up

to 5% wt of Ni

• Calcination at 850 °C for 5 h

• Catalyst was activated by reduction with H2 of

500 ml/min for 1 h to obtain pure Ni


Characterization of fresh catalyst

XRD analysis of fresh Mayenite (a) and NiO/Mayenite (b)

a) b)

• Successful synthesis of Mayenite (a)• Presence of residual Ca oxides (a)• Successful impregnation with Ni(NO3)2 to deposit NiO on the support (b)


Characterization of fresh catalyst (ii)

BET surface area (m2/g)

Fresh NiO/Mayenite 23

Ni/Mayenite after 3.5 h test 17

XRF of NiO/Mayenite (% wt)

Ca 29.03

Al 28.58

Ni 3.97


Characterization of fresh catalyst (iii)

SEM analysis of fresh Mayenite (a) and NiO/Mayenite (b)

• Porous structure of Mayenite (a)

• NiO grains of <1 µm deposited on the surface of Mayenite (b)

a) b)


Gas composition


Performance stabilized

after regeneration

Gas composition (ii)


Performance stabilized

after regeneration

TAR and CH4 CONTENT

Average values

• sampling collected any 30 minutes


TAR and CH4 conversion

First 3.5 hours of tests (before regeneration)


CH4 conversion tends to be stable around a low value

Possible catalyst deactivation:Carbon or Sulphur?

Sulphur deposit is negligble

Regeneration by TPO

Regeneration: temperature programmed oxidation (TPO)

Carbon content calculated 2360 µg C/gCAT


After TPO catalyst was reduced with 250 ml/minH2 for 1 h to eliminate NiO

TAR and CH4 conversion (after TPO)

3 hours of tests after regeneration


Conversion rates higher and

stable after regeneration

At the end of the tests the

measured C7+ < 0.0054% vol

Characterization after tests

XRD analysis of Ni/Mayenite after 3,5 hours tests of TAR steam reforming (a) and after regeneration with TPO (b)

No sulphur or carbon compounds identified in the catalyst after tests.

a) b)


No evident sintering after tests (b)

b)

Characterization after tests (ii)

a)


Sorption Enhanced Reforming

• Promising technology for high temperature decarbonisationof industrial plants

• In blast furnaces, a 50 MW demonstration plants was alreadybuilt

• Carbonatation takes place at 650°C, calcination at 900 °C (depending on pressure)




Dual Bed gasifier - in cooperation with TU Wien



SER at 650°

Conventional at 850°

New developments: Phytoremediation


New developments: Phytoremediation


Preliminary considerationsQuestion 1: Can gasification be a proper disposal technology?

Answer 1: Yes! The produced gas is as clean as the other feedstocks (pollutants are concentrated in the roots and negligible contents are measured in the tree body) and with a comparable HHV.

Question 2: How the contaminants affect the gasification?

Answer 2: The residual heavy metals can be easily concentrated in the traps present in the gasification plant. Furthermore, the presence of Ca and Mg have a catalysing effect reducing tar.

We can conclude that, after further validation with longer tests, PHYP could be considered for changing its classification from waste to renewable energy source

• Despite the good technological level of the biomass gasificationprocess, several improvements can be introduced to improve the process efficiency

• Such improvements involve the increase in the efficiency of the biomas-to-syngas conversion as well as the reduction of pollutantefficiency

• The use of advanced Ni-Mayenite catalyzer allows to reduce tar emission and to increase the HHV of the produced syngas

• SER technologies allow to reduce GHG emissions leading to a negative CO2 balance

• New developments can be considered: phyto-remediation

Conclusions


1. Borello D., Cedola L., Meloni R., Venturini P., De Filippis P., de Caprariis B., Frangioni

G.V., 2016, ‘A 3D packed bed model for biomass pyrolysis: experimental tests and model

calibration’, Applied Energy, Elsevier, 164, pp. 956-962

2. Di Carlo A., Borello D., Sisinni M., Savuto, E., Venturini, P., Bocci, E., Kuramoto K.,

2015, Reforming of tar contained in a raw fuel gas from biomass gasification using

nickel-mayenite catalyst, in International Journal of Hydrogen Energy, Elsevier, 40, pp.

9088–9095

3. Aghaalikhani A., Savuto E., Di Carlo A., Borello D., 2017, Poplar from phytoremediation as a

renewable energy source: gasification properties and pollution analysis, ICAE 2018, 21-24

August 2017

4. Savuto E., Borello D., Di Carlo A., Natali S., Pantaleo A., Rispoli F., Experimental study of

mayenite-based catalysts effectiveness in reducing pollution from biomass gasification in

fluidized bed reactors, GT57666, TurboExpo 2016, Seoul, South Korea, 13-17 June

5. Borello D., Di Carlo A., Marchegiani A.,Tortora E., Rispoli F., 2013, ‘Experimental and

Numerical Analysis of Steam-Oxygen Fluidized Gasifier Feeding a Combined SOFC/ORC

Power Plant’, ASME Turbo Expo 2013, 3-7 Giugno 2013. S. Antonio, Texas, USA, Best Paper

Award, Committee: Coal, Biomass and Alternative Fuels

Publications (Experiments)


1. Borello D., De Caprariis B., De Filippis P., Caucci M., Pantaleo A. M., Shah N., Modeling

and Experimental Study of a Small Scale Olive Pomace Gasifier for Cogeneration:

Energy and Profitability Analysis, Energies, 2017, 10, 1930

2. Di Carlo, A., Borello, D., Bocci, E., 2013, ‘Process simulation of a hybrid SOFC/mGT and

enriched air/steam fluidized bed gasifier power plant’, International Journal of

Hydrogen Energy, 38 (14) pp. 5857 – 5874

3. Borello, D., Rispoli, F., Venturini, P., and Saavedra G. Z., R., 2013, ‘Prediction of

multiphase combustion and ash deposition within a biomass furnace’, Applied Energy,

Elsevier, 101, pp. 413-422

4. Venturini, P., Borello, D., Hanjalic, K. and Rispoli. F., 2011, ‘Modelling of particles

deposition in an environment relevant to biomass-fired boilers’, Applied Thermal

Engineering, Elsevier, 49, pp. 131-138

5. Venturini P., Iossa C.V., Borello D., Lentini D. and Rispoli F., “Modeling of Multiphase

Combustion and Deposit Formation in a Biomass Fed Furnace”, Energy, Elsevier, 2010,

35, 3008-3021

DICMA, RESET and Universidad de Piura for TAR reforming

TU-WIEN and ENEA for Sorption Enhanced Reforming

CNR-IRSA, CNR-IBAF and ISPRA for phyto-remediation

Publications (Numerical)


Research Partnerships

Documents

Enhancement in biomass gasification: tar-reduction and sorption … · 2018-03-15 · biomas-to-syngas conversion as well as the reduction of pollutant efficiency • The use of advanced