Engineering Conferences InternationalECI Digital ArchivesBioEnergy IV: Innovations in Biomass Conversionfor Heat, Power, Fuels and Chemicals Proceedings

Spring 6-11-2013

Clean hydrogen rich gas from catalytic steamgasification of biomassSergio RapagnaFaculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo

Annalisa D'OrazioFaculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo

Katia GalluciDepartment of Industrial Engineering, Information and Economy, University of L’Aquila

Manuela Di MarcelloFaculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo

Manfred NackenPall Filtersystems GmbH Werk Schumacher

See next page for additional authors

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Recommended CitationSergio Rapagna, Annalisa D'Orazio, Katia Galluci, Manuela Di Marcello, Manfred Nacken, Steffen Heidenreich, and Pier Foscolo,"Clean hydrogen rich gas from catalytic steam gasification of biomass" in "BioEnergy IV: Innovations in Biomass Conversion for Heat,Power, Fuels and Chemicals", Manuel Garcia-Perez,Washington State University, USA Dietrich Meier, Thünen Institute of WoodResearch, Germany Raffaella Ocone, Heriot-Watt University, United Kingdom Paul de Wild, Biomass & Energy Efficiency, ECN, TheNetherlands Eds, ECI Symposium Series, (2013). http://dc.engconfintl.org/bioenergy_iv/20

AuthorsSergio Rapagna, Annalisa D'Orazio, Katia Galluci, Manuela Di Marcello, Manfred Nacken, SteffenHeidenreich, and Pier Foscolo

This conference proceeding is available at ECI Digital Archives: http://dc.engconfintl.org/bioenergy_iv/20

CLEAN HYDROGEN RICH GAS FROM CATALYTIC STEAM GASIFICATION OF BIOMASS

Sergio Rapagnà, Annalisa D’Orazio, 1Katia Gallucci, Manuela Di Marcello, 2Manfred Nacken, 2Steffen Heidenreich and 1Pier Ugo Foscolo

Faculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo,

Via Carlo R. Lerici 1, 64023 Mosciano Sant’Angelo, Teramo, Italy

1Department of Industrial Engineering, Information and Economy, University of L’Aquila,

Via Campo di Pile, Zona industriale di Pile 67100 L’Aquila, Italy

2Pall Filtersystems GmbH Werk Schumacher

Zur Flügelau 70, 74564 Crailsheim, Germany

IntroductionBiomass gasification is a thermo-chemical conversion process which produces a

fuel gas rich in hydrogen and carbon monoxide, with a significant content of

methane and carbon dioxide. Steam is also present in the producer gas,

in addition to organic (tar) and inorganic (H2S, HCl, NH3, alkali metals)

impurities, and particulate.

Gas cleaning is normally done by filtration and scrubbing of the producer gas, to

drastically reduce particulate and tar content.

Biomass particles

+ heat

Gas + hydrocarbons

+ steam

H2, CO, CO2, CH4, CnHm

To increase the efficiency of the utilization of thermal and

chemical energy of the producer gas, hot gas cleaning and

conditioning systems (abatement of particulate content and tar

conversion at a temperature close to the gasification temperature)

should be developed and implemented through a compact design

and reliable and simple-to-operate equipment.

Process simplification and intensification could play a very

important role to a real breakthrough in the utilization of biomass

in general, and specifically of gasification plants.

Catalytic filter candles have been proposed as an alternative, very

promising technology to be coupled to biomass gasification

processes (UNIQUE and UNIfHY Projects).

T2 T3

T1

T4

T5

DP1 DP1 DP1

Pump

Ciller

Gas

Gasmete

r

Gas Analysers

Ciller

Pump

Heater

Water

Air

N2

H2 CO, CO2

CH4

H2S NH3

The organic component (tar) in the

condensate samples was determined by

Total Organic Carbon (TOC) analysis

Tar fraction sampled in 2-

propanol, according to the

Technical Specification

CEN/TS 15439

The composition of the tar

fraction was determined by

GCMS or HPLC/UV

Experimental apparatus

870 mm

260 mm

Fluidized

bed

gasifier

+

Catalytic

filter candle

Candle

• Outer diameter= 60 mm

• Inner diameter= 40 mm

• Total length 450 mm

• Filtering length 400 mm

Process conditions

• Biomass feed rate = (8 ÷ 10) g/min

• Steam flow rate = (7.7 ÷ 9.5) g/min

• Steam/biomass dry = (0.9 ÷ 1.11)

• Bed temperature = (800 ÷ 815) °C

• Reactor outlet temperature = (760 ÷ 800) °C

• Olivine dm= 350micron

• Biomass dm= 1100micron

Biomass properties

• Dry matter = 92.3%

• Ash= 1.1%

• Volatile matter= 71.9

• Fixed carbon= 19.5

N260912,1 : Al2O3 based hot filter candle of new improved candle

support type (UHT) and with an Al2O3 outer membrane.

N051112,1 : Al2O3 based hot filter candle of new improved candle

support type (UHT) and with an Al2O3 outer membrane.

C280912,1 : catalytically activated Al2O3 filter candle of new improved

candle support type (UHT) with an Al2O3 outer membrane. MgO-

NiO catalytic layer system was applied.

C181212,1 : catalytically activated Al2O3 filter candle of new improved

candle support type (UHT) with an Al2O3 outer membrane and

with integrated catalytic ceramic foam. MgO-NiO catalytic layer

system was appliedon the catalytic filter candle support; a MgO-

Al2O3-NiO based catalytic layer system was applied on the

integrated catalytic ceramic foam.

Filter Candles

C1/NC C1/NC C3/C C4/CF

Candle N260912,1 N051112,1 C280912,1 C181212,1

Type No catalytic No catalytic Catalytic Layer

Catalytic +

catalytic foam

Legend

Test code 0101 0102 0103 0104 0105 0106 0107 0108 0109 0110 0111 0112 0113

Candle C1/NC C1/NC C3/C C3/C C3/C C3/C C3/C C4/CF C4/CF C4/CF C4/CF C4/CF C4/CF

Test number I I I II III IV V I II III IV V VI

Biomass feed

rate, [g/min] 8,1 8,1 8,1 8,1 8,1 10 10 10 10 10 10 10 10

Steam/biomass

dry 1,11 1,15 1,13 1,19 1,18 1,03 1 0,94 0,94 0,95 1,08 1,12 1,10

Total

gasification

time [min] 247 313 210 420 420 183 180 190 240 111 180 300 239

Tests

0

10

20

30

40

50

60

H2 CO2 CO CH4

USED

FRESH

N260912,1 / N051112,1 : Al2O3 based hot filter candle of new improved candle support type

(UHT) and with an Al2O3 outer membrane

No-catalytic Candle

Test 0101 0102

Candle C1/NC C1/NC

Bed state USED FRESH

Bed using-time >10:00:00 0

Biomass feed rate, g/min 8.1 8.1

Steam/biomass dry 1.11 1.15

Condensate [g/min] 6.09 6.49

Water conversion % 29 25.2

Gas yield, Nm3/kgdaf 1.76 1.41

Tar content, g/Nm3, by TOC 0.049 0.651

Tar content, g/Nm3 by GCMS 5.958 ------

H2

(vol% dry N2 free) 55 51.5

CO2

(vol% dry N2 free) 22,5 25

CO

(vol% dry N2 free) 20 18

CH4

(vol% dry N2 free) 2,5 5,5

N260912,1 / N051112,1 : Al2O3 based hot filter candle of new improved candle support type

(UHT) and with an Al2O3 outer membrane

X-Ray Fluorescence Measured - w%

K 4,03

Si 1,64

Ni 0,11 (expected < 0,03)

Biomass composition mg / Kg_dry

K 5237,9

Ni 16,7

Olivine composition w%

SiO2 42

NiO 0,3

No catalytic Candle 1st Test - Ni %

Test 0106 0107

Candle C3/C C3/C

Bed state USED FRESH

Bed using-time 23:30:00 0

Biomass feed rate, g/min 10 10

Steam/biomass dry 1.03 1

Condensate [g/min] 6 6.36

Water conversion % 36.8 31

Gas yield, Nm3/kgdaf 1.63 1.48

Tar content, g/Nm3 by TOC 0.022 0.120

Tar content, g/Nm3 by GCMS 1.071 2.545

H2

(vol% dry N2 free) 54 52

CO2

(vol% dry N2 free) 22 24

CO

(vol% dry N2 free) 19 18

CH4

(vol% dry N2 free) 5 6

C280912,1 : catalytically activated Al2O3 filter candle of new improved candle

support type (UHT) with an Al2O3 outer membrane. MgO-NiO catalytic

layer system was applied.

0

10

20

30

40

50

60

H2 CO2 CO CH4

Catalytic Candle

USED

FRESH

Catalytic Candle

C181212,1 : catalytically activated Al2O3 filter candle of new improved candle support type

(UHT) with an Al2O3 outer membrane and with integrated catalytic ceramic foam.

MgO-NiO catalytic layer system was appliedon the catalytic filter candle support;

a MgO-Al2O3-NiO based catalytic layer system was applied on the integrated

catalytic ceramic foam

0

10

20

30

40

50

60

H2 CO2 CO CH4

Catalytic Candle + Catalytic Foam

USED

FRESH

Catalytic Candle + catalytic foam

Test 0108 0112

Candle C4/CF C4/Cf

Bed state USED FRESH

Bed using-time 31:16:00 0

Biomass feed rate, g/min 10 10

Steam/biomass dry 1.12 0.94

Condensate [g/min] 6.1 5.64

Water conversion % 41 33.5

Gas yield, Nm3/kgdaf 1.84 1.48

Tar content, g/Nm3 by TOC 0.010 0.062

Tar content, g/Nm3 by GCMS 1.311 0.142

H2

(vol% dry N2 free) 55.5 51

CO2

(vol% dry N2 free) 20 22

CO

(vol% dry N2 free) 21.5 22

CH4

(vol% dry N2 free) 3 5

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

FRESH

USED

BED USED FRESH

COMPOUNDSTAR

content

[g/Nm3]

TAR

content

[g/Nm3]

ACENAPTHYLENE 0.004 0.010

FLUORENE 0.002 0.006

PHENANTRENE 0.006 0.023

ANTHRACENE 0.006 0.004

PYRENE 0.000 0.003

PHENOL 0.000 0.000

NAPTHALENE 0.037 0.466

STYRENE 0.000 0.045

XYLENE 0.000 0.040

TOLUENE 0.087 0.714

TOTAL 0.142 1.311

0.00

0.01

0.01

0.02

0.02

0.03

GCMS- measurement on catalytic candle with catalytic foam

(C181212,1) :

TAR abatement (GCMS)

H2

CO2

CH4

CO

0

10

20

30

40

50

60

0 60 120 180 240 300 360 420 480 540 600

time, min

% b

y v

olu

me

nN

2fr

ee

0

20

40

60

80

100

0 60 120 180 240 300 360 420 480 540 600

time, min

Pre

ssure

dro

p t

hro

ug

h t

he

filt

er, c

m o

f H

2O

Gas composition and pressure drop for the catalytic candle with catalytic foam

with used olivine

Candle None C1/NC C1/NC C3/C C3/C C4/CF C4/CF

Bed state best - value USED * FRESH USED FRESH USED FRESH

Gas yeld [Nm3(dry

N2free)/kg daf]1 1.76* 1.41 1.63 1.48 1.84 1.48

H2 [%vol (dry gas,

N2free)] 39 55* 51.5 54 52 55.5 51

CH4 [%vol (dry gas,

N2free)] 10 2.5* 5.5 5 6 3 5

Water conversion [%] 16 29* 25.2 36.8 31 41 33.5

TAR content g/Nm3

by TOC3.7 0.049* 0.651 0.022 0.12 0.01 0.062

TAR content g/Nm3

by HPLC/UV or GCMS

7

(HPLC/UV)

5.958

(GCMS)-------

1.071

(GCMS)

2.545

(GCMS)

0.14

(GCMS)

1.31

(GCMS)

*Ni contamination

Candles performance comparison

Conclusions

The innovative concept of integrating a catalytic hot gas filter in

the freeboard of a fluidized bed gasifier has been tested. This

promising technology results in greatly increased gas and

hydrogen yields, as the same time giving rise to significant power

plant simplification and intensification

The best results, in respect to the gasification without candle,

show:

– Hydrogen content increases more than 40%

– Methane content decreases more than 70%

– Gas yield increases more than 80%

– Water conversion increases more than 2 times

– TAR content decreases more than 1 order

steam

exhaust gases

air

biomas

clean hydrogen rich gas

air

steam

hot water

exhaust gas

Tank you for your attention.