Chemical Process Engineering Research Institute (CPERI)/Center for Research and Technology Hellas (CERTH) Conversion of Biomass to Fuels and Chemicals via Thermochemical Processes Angelos A. Lappas Research Director CPERI/CERTH P.O. Box 361 GRGR-570 01 Thermi--Thessaloniki, Greece Thermi

EUROBIOREF Summer School September 1818-24, 2011 Castro Marina Lecce, Italy

OUTLINE   

Introduction--Biomass/Biofuels Introduction Biomass Pyrolysis Process Biomass Catalytic Pyrolysis Process

       

Process Description Experimental results and discussion Catalyst effects Conclusions

Upgrading the Bio Bio--oil by downstream catalytic routes Upgrading by HP Upgrading by FCC Upgrading by Co Co--processing

CPERI/CERTH

Biomass Utilization Heat

Electricity

Fuel Conversion Process Feedstocks

Chemicals CPERI/CERTH

Why Biofuels? Motivation ...

 Sustainability – Energy Security  Reduction of Greenhouse gas (GHG) emissions  Reinforce agricultural economy – Introduction of competitive energy crops – Development of new job openings – Support other industries (sugar, paper etc) CPERI/CERTH

European Roadmap for Fuels (EUCAR)

Source: European Biofuels Technology Platform (WG3) Report: 02.08.2007 CPERI/CERTH

1st Generation Biofuels  Biodiesel from transesterification of vegetable oils  Bioethanoll from sugars Advantages  Well tested technology  High quality products with excellent burning characteristics – High octane number, small cetane number

Disadvantages  High production cost – Limited type of biomass employed  Competition with food-crops  Dependence on legislation  Questions regarding sustainability

CPERI/CERTH

2nd Generation Biofuels  Biofuels from thermo-chemical processes Advantages  Feedstock: Non-edible part of biomass  Compatible products with today’s fuels  Utilization of existing units  High conversion of carbon into final product  Small operational cost

Disadvantages  High investment cost  Necessity to construct large scale units of significant capacity  Essential availability of large amounts of biomass

CPERI/CERTH

BIOMASS FAST PYROLYSIS PROCESS

 Biomass pyrolysis: a basic biomass thermo-chemical process for the production of liquids, solids and gaseous products  For biomass heating a solid heat carrier is used

CPERI/CERTH

Biomass pyrolysis: use of all biomass

Crude Oil 100$/bbl ~ 13 €/GJ 75 $/bbl ~ 10 €/GJ 60 $/bbl ~ 8 €/GJ 15 $/bbl ~ 2 €/GJ

Oils Sugars

~ 16 €/GJ ~ 20 €/GJ ~ 8 €/GJ

Brazil

Cellulose “Biomass Waste” ~70%

Hemi - Cellulose

< 3 €/GJ

Lignin CPERI/CERTH

PYROLYSIS CHARACTERISTICS 

Slow pyrolysis (mainly in fixed beds):  Heating rates: 5-7 K/min  Less liquids (30-40%wt) and more char (30-40%wt)

 Fast pyrolysis:  High temperature process in the absence of air  Very high heating rates (>300°C/min) and heat transfer (requires ground of biomass)  Carefully temperature control  Rapid cooling  Liquid: 70%, gases:15%, char:15%

Bio oil has an energy density of 20 GJ/m3 compared to 4 GJ/m3 for wood chips and the oil's ash content is 100 times lower than that of biomass. CPERI/CERTH

Pyrolysis Reactions High T

Low Temp
400)

5.00%

Zirconia Titania (80) 0.00% 0.00%

5.00%

10.00%

15.00%

20.00%

25.00%

30.00%

35.00%

40.00%

45.00%

Organic Yield (wt% on biomass)

 Biooil cracking leads to less oxygen content in biooil  Different quality biooils can be produced with different catalysts  Enhanced cracking yields less organic oil and more coke, CO, CO2 and water CPERI/CERTH

Bench - Pilot Scale Correlation Organic liquid yield vs Oxygen content

Oxygen content of organic liquid, wt%

45.00 40.00 35.00 30.00 25.00

Pilot Plant

20.00

Bench Scale

15.00 10.00 5.00 0.00 0.00

10.00

20.00

30.00

40.00

50.00

60.00

Organic liquid, wt% on biomass

 Same Deoxygenation – Cracking trend for both scales  Greater Deoxygenation and biooil yields for Pilot scale due to better heat transfer, residence times and C/BM ratio CPERI/CERTH

Bench - Pilot Scale Correlation Organic liquid yield vs Oxygen content

Oxygen content of organic liquid, wt%

45.00 40.00 35.00 30.00 25.00

Pilot Plant

20.00

Bench Scale

15.00 achieved biooil

10.00 5.00 0.00 0.00

10.00

20.00

30.00

40.00

50.00

60.00

Organic liquid, wt% on biomass

 Same Deoxygenation – Cracking trend for both scales  Greater Deoxygenation and biooil yields for Pilot scale due to better heat transfer, residence times and C/BM ratio CPERI/CERTH

Bio--Oil Analysis (2DGC/TOFMS) Bio Thermal Biooil

Catalytic Biooil

CPERI/CERTH

Conclusions:: Biomass Catalytic Pyrolysis Conclusions

 Biomass Catalytic Pyrolysis significantly changes bio oil chemical composition  Need for optimization of catalysts and operating conditions  Key to catalyst formulation are: Surface area, Acidity and Pore size distribution

CPERI/CERTH

Upgrading the Biomass Fast Pyrolysis Liquids (BFPL)

CPERI/CERTH

Bio--oil UPGARDING PROCESSES Bio

 Hydroprocessing (HP) of BFPL – Catalytic Hydroprocessing (CHP) – Thermal Hydroprocessing (THP)  Catalytic Cracking of BFPL

CPERI/CERTH

HYDROPROCESSING (HP) BFPL  Tests Performed in Veba Oil  Use of an Eucalyptus Biooil feed  Catalytic HP (CHP) – Experimental Unit • Down flow Fixed bed Reactor (ID=3 cm, L=1123cm) • Catalyst tested: Commercially available NiMo, CoMo • Variables: T, WHSV

 Thermal HP (Veba Combi Cracking Process) – Experimental Unit • Slurry reactor (ID=4.5 cm, L=400cm) • T=327°C • Variables:T, WHSV

CPERI/CERTH

Results of BFPL HP

 Different severities of HP by varied T, WHSV  Degree of deoxygenation (DeO) was measured: – Thermal:78-85% – Catalytic:88-99.9%

 Catalytic HP run time only 100 hrs (operating plugging problems) – This was fully confirmed in BIOCOOP

 Thermal HP run time 1 week w/o operating problems

CPERI/CERTH

Effect of DEO rate on product yield in THP

oil

H2O

gas

H2 consumption

60 Yield [wt%]

50 40 30 20 10

THP

CHP

0 75

80

85 90 Deoxygenation Rate [wt%]

95

100

CPERI/CERTH

Effect of DEO rate on Product Properties in THP

oxygen content

density 1.1

8

1

6

0.9

4

0.8

2

0.7

THP

CHP

0 75

80

3

10

density [g/cm ]

C/H [wt%/wt%], O [wt%]

C/H

85

90

95

0.6 100

Deoxygenation Rate [wt%]

CPERI/CERTH

Quality of Thermally HP BFPL Light fraction

Heavy fraction

70

30

C

82.2

84.4

H

10.7

9.4

S

0.01

0.01

N

1.15

0.42

O

6.4

4.9

H2O

0.99

Density

0.942

%wt of total product Elemental Analysis (%wt)

1.036

Distillation (°C/%wt) 500

11 CPERI/CERTH

BFPL CATALYTIC CRACKING

 Literature studies using: – HZSM-5 catalysts – FCC catalysts  Tests showed very high coking (around 20%wt)  Blending very difficult due to minor miscibility of BFPL/HC

CPERI/CERTH

Co-Processing Upgraded Biomass Fast Pyrolysis LiquidsBFPL

CPERI/CERTH

TECHNOLOGY INVESTIGATED IN CPERI FOR NON CATALYTIC BIOOIL

Light Oil Hydrogen Low Severity THP

Separation

BFPL Heavy Oil FCCU

Fuels

VGO Concept: Replace Resid with BFPL in Conventional FCCU

CPERI/CERTH

CO PROCESSING THPTHP-BIOOIL IN FLUID CATALYTIC CRACKING UNITS

 Experiments performed in bench and pilot scale  Use of THP-Bio-oil from low severity HP (80%DeO)  Bench scale studies – Catalyst evaluation  Pilot scale studies – Validation of the proposed technology

CPERI/CERTH

BENCH SCALE TESTING  Target: to select catalyst with low coke make  Feedstock: THP-BFPL/LCO mixture (15/85 w/w): – MCRT=0.4

 Bench scale unit: fixed bed (modified MAT)  Testing of 2 commercially available catalysts with different Re content (ReUSY1, ReUSY2)  Experimental conditions: T=500-550°C, C/O=3-6

CPERI/CERTH

Bench Scale Experimental Results 2.3

35

2 Gasoline Yield (wt %)

Coke on Catalyst (wt %)

Catalyst: ReUSY

1.7 1.4 1.1 0.8 0.5

30 25 20 15

Catalyst: ReUSY

10

1

2

3

4

5

6

7

40

Catalyst to Oil Ratio, (C/O)

44

48

52

56

60

Conversion (wt %)

 Very promising results from Bench scale studies – A ReUSY catalyst was the best for low coke selectivity – Coke on catalyst was less than 1.5%wt (coke yield 3-6%wt) – Gasoline yield 20-25%wt

CPERI/CERTH

PILOT SCALE TESTING  Tests in a fully circulating FCC pilot plant unit  Use of an Ecat from a Greek refinery (TSA=158m2/g)  Use of a conventional VGO as base feed  Co-processing: 85%VGO+15%(LCO+THP Bio-oil)  THP Bio-oil was 15% in the LCO  Tests with only VGO+15%LCO for comparison

CPERI/CERTH

FCC Pilot Plant Experimental Results

35

50

VGO + 15% LCO VGO + 15% (LCO+Biooil)

30

46 LCO yield, wt%

C5-430°F yield, wt%

48 44 42 40 38 36 VGO + 15% LCO

32

VGO + 15% (LCO+Biooil)

10

30 55

60

65 70 Conversion, wt%

20 15

34

50

25

75

80

50

55

60

65 70 Conversion, wt%

75

80

 Effect of Bio-oil co-processing – No operating problems in the pilot plant – Positive effect in gasoline and LCO selectivity – Coke increases 0.5%wt – Conversion decreases 2 units at the same C/O – Gasoline contains more aromatics CPERI/CERTH

TECHNOLOGY INVESTIGATED IN CPERI FOR CATALYTIC BIOOIL

 Hydroprocessing  Catalytic Cracking  Unpublished results (Acenet/Hecabio) show very good performance of both processes

CPERI/CERTH

CONCLUSIONS  Upgrading of bio-oil is a very complicated task and R&D on catalysis/process is required

 For the conventional bio-oil hydtrotreating seems unavoidable to remove oxygen

Thermal hydrotreating has less operating problems  The use of a catalytic bio-oil helps to use less severe conditions in both HP and FCC

a catalytic biooil with less than 20% oxygen is now feasible  Research work is needed: Fundamentals on biomass catalytic pyrolysis (mechanisms/kinetics) Optimization of catalyst properties Upgrading of catalytic bio-oil through HP/FCC/esterification Advanced characterization of bio-oil Separation of high added value chemicals chemicals CPERI/CERTH