fast pyrolysis and hydrothermal processing · 2019-11-08 · your logo this project has received...

Your logo

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 764089

Fast pyrolysis and hydrothermal processingRobbie Venderbosch, BTG

ABC Salt Summer School – Aston University, 12-14 August ‘19

Your logo

Content

• Principles of fast pyrolysis

• Why fast pyrolysis

• Bio-oil properties and applications

• Commercial implementation of fast pyrolysis: Empyro

• Biofuel prospects in fast pyrolysis

• Refinery co-feed

• Hydrotreatment

• Take home message

Your logo

Fast pyrolysis: introduction

Principle of fast pyrolysis

• The decomposition of biomass by heating in an oxygen-free or oxygen-limited environment

• Results in the production of three phases: gas, condensable vapours (leading up to bio-oil) and char

(biochar)

• Gases and volatiles driven out of the biomass particles due to pressure built up in the particle

• Fast reactions, but in practice heat and mass transfer limitations occur affecting product

distribution

BiomassLiquid

(bio-oil)

Solid

fraction

GasHeat

Your logo


Based on the process condition (temperature, heating rate and atmosphere) the following conversion

processes can be distinguished:

Type Temp (°C) Vapor residence time

Heat source Char yield (wt.%)

Liquid yield(wt.%)

Gas yield(wt.%)

Slow pyrolysis 300-500 5-30 min external/ internal (oxygen addition)

35 % 30 % 35 %

Intermediate pyrolysis

500 10-20 s external 20 % 50 % 30 %

Fast pyrolysis 500-600 1 s external 12 % 75 % 13 %

Torrefaction (partial pyrolysis)

< 300 minutes external 80 % 5 % 15 %

Gasification > 750 10-20 s internal (oxygen addition)

10 % 5 % 85 %

Your logo


In fast pyrolysis, we want to maximize the yield in volatiles (minimize

char/gas)

Hence, suppressing secondary pyrolysis reactions:

• Temperature ~ 500°C

• Fast heating of particles (up to 100°C/s)

• So small particles are only suitable (max. 3 mm need to grind

biomass)

• Pressure = 1 atm.

• Short vapor residence time (<2 s)

• Short but sufficient biomass residence time (>10 s)

Effect of pyrolysis temperature on gas/liquid/char yield (fluidized bed, 3 mm

pine wood as feedstock)

Your logo

Fast pyrolysis: why ?

Fast pyrolysis: Benefits

• Energy densification: Bio-oil, on a mass basis, has a HHV (higher

heating value) equal to its parent biomass (18 ~ 20 MJ/kg for

wood and wood bio-oil). However, density of bio-oil is ~ 1.1 kg/L –

as such HHV on a volume basis can increase

• A liquid (bio-oil) is easier and more cheap to handle (transport,

storage) than a bulk solid (parent biomass): local processing of

biomass into liquid and central collection of liquid: cheaper

logistics

• The bio-oil is virtually free from mineral compounds

• Decoupling of the conversion of biomass and the application of

the bio-oil, both in time and space

• Flexibility in applications (see later)

Petroleum

refinery

Biomass

production area

Biomass

Stabilised bio-oil

Chem

icals

Fuels

Pyrolysis unit

Pyrolysis unit

Pyrolysis unit

Mobile

pyrolysis unit

Pyrolysis unit

Pyrolysis unit

Crude bio-oil

Pyrolysis unit

Bio-oil upgrading/

bio-oil refining

Your logo

Fast pyrolysis: properties of the bio-oil

• Combustible, HHV ~ 18 MJ/kg (half of that of

petroleum)

• Rich in oxygenated organic compounds (same amount

of O as the original biomass)

• 10 to 15 wt% water

• Highly corrosive, pH ~ 2

• Non distillable

• Unstable (‘ageing’ = polymerization bio-oil

constituents during storage, deteriorating quality of

the oil)

• Immiscible with hydrocarbons (unless use of

surfanctans)

• Low cetane number (10 ~ 25)

Your logo


Comparison with heavy fuel oil

Your logo


Chemical

composition(maximally reported

concentrations)

Cellulose/hemicellulose derived Lignin derived

Compound wt.% Compound wt.%

Levoglucosan 30.4 Formaldehyde 2.4

Hydroxyacetaldehyde 15.4 Phenol 2.1

Acetic acid 10.1 Propionic acid 2.0

Formic acid 9.1 Acetone 2.0

Acetaldehyde 8.5 Methylcyclopenten-2-one 1.9

Furfurylalcohol 5.2 Methyl formiate 1.9

Catechol 5.0 Hydroquinone 1.9

Methylglyoxal 4.0 Acetol 1.7

Ethanol 3.6 Angelica lactone 1.6

Cellobiosan 3.2 Syringaldehyde 1.5

1,6-anhydroglucofuranose 3.1 Methanol 1.4

Your logo

Fast pyrolysis: a versatile application platform

Bio-oilTurbine or diesel

engine fuel

Orenda 2.5 MW turbine

Co-feeding in

boilers

Upgrading,

refinery co-feedDrop-in biofuels

Syngas

platform

Gasification

Whole fractions,

i.e. sugar

Specific

compounds

Fermentation (hybrid

processing)Extraction

Char

Solid fuel

Biochar as soil

amender

Absorbent, filter

substrate

Your logo

Fast pyrolysis: commercial implementation by BTG

Employees BTG B.V.

Employees BTG

B.V.

Employees BTG BV

Company Profile BTG

RTDConsultancy

3rd parties

3rd parties

Biomass Technology

Holding BVEnschedeAmsterdam

Rotterdam

Belgium

Groningen

Berlin 445 kmParis 485 kmLondon 490 km

Amsterdam 160 km

Your logo


Development timeline

1987

Knowledge transferred from UT to BTG

Rotating cone reactor ‘invented’ at University of Twente (UT)

1993

1994

1998

2005

2007

2015

2014

Delivery semi-continous test unit (50 kg/hr) to Shenyang (China)

Start-up of 200 kg/hr FP pilot plant in BTG Laboratory

Start construction 120 t/d Empyro plant in Hengelo (NL)Long-term FPBO supply contract signed

Delivery of 50 t/d FP-plant to Malaysia

Establishment of BTG Bioliquids BV to commercialize BTG Fast Pyrolysis technology

2009 Establishment of Empyro BV to demonstrate FP technology

2018Co-production of FPBO, process steam and electricity3 years operational experience: production and use

EmpyroNetherlands

2004 Large-scale co-firing test at Harculo Power Plant

Start-up Empyro plant & Process steam boiler at FrieslandCampina

2013

research

development

Roll-out

1989

Your logo


Biomass5 tons/hr (moisture ~ 5 wt%)

Pyrolysis oil ~ 3,3 t/hr~ 15 MW

650 kWe

Electricity production

~ 40% backto process

~ 60%to grid

~ 6.5 MW steamto AkzoNobel

~ 1 MW steamback to dryer

Your logo


Empyro efficiency

Overall Efficiency : 85 %

Biomass : 24

Hot condensate : 1.6Electricity : 0.3

Electricity : 0.3

Losses : 2.9Steam : 8

Oil : 14.4

In : 25.9

Your logo


EMPYRO – status after 14 quarters of operation (June 2018)

Commissioning

• March 2015: First litres of oil; delivery steam to AkzoNobel;

• August 2015: delivery FPBO to FrieslandCampina

• October 2016: Steam turbine commissioned

Production

• Scale up RCR very successful

• 7 operators; One operator to run the plant at night;

• ~ 30 million liters produced (3 years)

• Runtime and production capacity still (gradually) increasing

• Oil yield around design value 65 wt%; quality excellent from start

• 3.3 tons of oil per hour + 7.4 MWth steam; 650 kWe Electricity (near 90%

heat efficiency)

Economics

• Overall investment within original budget

• Actual oil production costs in line with predictions

Your logo


EMPYRO – status after 14 quarters of operation (June 2018)

Your logo

Fast pyrolysis: biofuel prospects

Fast pyrolysis seems to be the cheapest option to produce 2G biofuels

Also supported by recent information and reports Provided by BETO Bioenergy Technologies Office (2015 until now)

Your logo

Production cost

Landalv & Waldheim, 2017, Building up the future, cost of biofuel, EC sub group Advanced Biofuels (SGAB)IRENA: INNOVATION OUTLOOK, 2016 Advanced Liquid Biofuels

Data by technology providersData adjusted by SGAB Internal Renewable Energy Arena


Your logo


Your logo

Investment cost

Landalv & Waldheim, 2017, Building up the future, cost of biofuel, EC sub group Advanced Biofuels (SGAB)IRENA: INNOVATION OUTLOOK, 2016 Advanced Liquid Biofuels


Your logo

Gasification routes

2ndG Fermentation

KiOR

IH2

Pyrolysis HDO

Pyrolysis only

HTL only

HTL + HDO


Specific investment cost

Your logo


Pyrolysis

Plant

Oil Refinery

Diesel

LPG

x times 20-

50 kton/y

Distillation

Hydrotreater

Vacuum

Gas Oil

Co-refining FPBO in FCC enables production of 2nd generation bio-fuels while utilizing

existing refining infrastructure.

Fast Pyrolysis Oil

Crude Oil

Gasoline

Co-FCC Route

Drop-in biofuels from pyrolysis through co-processing

Your logo


FCC unit in a petrorefinery

Feedstock VGO

Yields, wt%

CO 0.1

CO2 0.1

Water 0.0

Dry Gas 3.9

LPG (C3-C4) 15.2

Gasoline (C5-220°C)

40.4

Diesel (220-344°C)18.1

Bottoms (+ 344°C) 14.8

Coke 7.4

Your logo


Co-processing of FPBO results

Feedstock VGO 90% VGO +

10% Bio-oil

80% VGO +

20% Bio-oil

Yields, wt%

CO 0.1 1.9 3.1

CO2 0.1 0.5 0.8

Water 0.0 2.3 7.3

Dry Gas 3.9 2.8 2.5

LPG (C3-C4) 15.2 12.9 9.9

Gasoline (C5-220°C) 40.4 40.7 37.7

Diesel (220-344°C) 18.1 17.4 16.5

Bottoms (+ 344°C) 14.8 14.0 13.7

Coke 7.4 7.5 8.5

Mass balance – 95 – 98 wt.% Oxygen balance - 70 - 87 wt. %

Your logo


But: can we do better than co-feeding whole FPBO ?

What we do in seconds is what nature does in millions of years

Pyrolysis oil crude oil

‘black dirty liquid’

… but much worse….

Your logo


Biomass Pyrolysis Oil

Hemi-cellulose

Cellulose

Lignin

Acids, Carbonyls

Sugars / Syrup

Pyrolytic Lignin

Overall Composition C2H5O2

Oxygen content 45 - 50 %

pH 2,5 - 3,5

Density 1.15 kg/l

Heating Value 16 -18 MJ/kg

Viscosity 25 cP

Ash < 0.1 wt.%

Pyrolysis oil crude oil

Syrup in which lignitic fragments are

emulsified

Synergetic effects

are limited

if not present at all!

Your logo


Hydrotreating

• Removal of oxygen in pyrolysis oil using high pressures, high temperatures (250 to 400°C) and hydrogen gas

• Using a catalyst: (1) Sulfided CoMo and NiMo catalysts or (2) Noble and transition metals on carbon or on alumina as a support

• Able to remove all oxygen in pyrolysis oil (not possible using catalytic fast pyrolysis alone) !

H2

Catalyst

Hydrodeoxy

genation

Upgraded

Bio-oil

Crude bio-oil

Your logo


0.0

0.4

0.8

0.0 1.0 2.0

O/C

(-)

H/C (-)

lignin_Oasmaa phenolcharcoal RepCrude oil HTUPyrolysis oil DieselRuG HPPTDCO Baldauf and Balfanz (1997)Churin et. al. (1988) BaldaufConti et al. (1997) Samolada et al. (1998)Elliott (2007) Kaiser (1997)Zhang University of SassariALBANY ElliottElliott 2 Elliott 3Gevers et al. Elliott 4Elliott 5 - Mild HDO Elliott 6 - 1st stage

charcoal

Stabilization of biomass‐derived pyrolysis oils. J. Chem. Technol. Biotechnol., 2010, 85 (5): 674-686

Hydrotreating, literature data

Your logo



Hydrotreating, literature data and own data

0.0

0.4

0.8

0.0 1.0 2.0

O/C

(-)

H/C (-)

lignin_Oasmaa phenol

charcoal Rep

Crude oil HTU

Pyrolysis oil Diesel

RuG HPPT

DCO Baldauf and Balfanz (1997)

Churin et. al. (1988) Baldauf

Conti et al. (1997) Samolada et al. (1998)

Elliott (2007) Kaiser (1997)

Zhang University of Sassari

ALBANY Elliott

Elliott 2 Elliott 3

Gevers et al. Elliott 4

Elliott 5 - Mild HDO Elliott 6 - 1st stage

Elliott 7 Elliott 8 - two stage

Elliott 9-white wood mild HDO Bio-oil dry

Lignin Elliott Bagasse

HPTT Pyrolysis oil

Samolada et al. (1998) water removal

Picula

charcoal

water removal

Your logo



Hydrotreating, own data

0.0

0.4

0.8

0.0 1.0 2.0

O/C

(-)

H/C (-)

charcoal

water removal

Picula

charcoal

water removal Dehydration225-275oC

Hydrogenation (Hydro)crackingHydrodeoxygenation>325oC

Hydrogenation <250oC

Your logo



Hydrotreating, own data

Your logo


Deo

xyge

nat

ion

(%)

‘Carbohydrate’ hydrogenation

‘Carbohydrate’ deoxygenation -dehydration

Olefins and aldehyde hydrogenation, lignin mild cracking

Lignin (hydro)cracking

Improved liquid = likely an oil

‘SPO’

‘SDPO’

Your logo


Liquid conversion: sugar chemistry versus lignin chemistry

Pyrolysis Stabil. / partial deoxy.

PL

H2

‘Full’ Deoxyg.

water

1stG Picula SotA CoMo/NiMo-s

water

gas

gas

SUGAR CHEMISTRY LIGNIN CHEMISTRY (petro?)

100-200 L H2/kgPL

200-600 L H2/kgPL

Stabilisedpyrolysis oil

Stabilised deoxygenated pyrolysis oil

Your logo


Let’s recall co-feeding in FCC

Pyrolysis

Plant

Oil Refinery

x times 20-

50 kton/y

Distillation

Hydrotreater

Vacuum

Gas Oil

Co-refining FPBO in FCC enables production of 2nd generation bio-fuels while

utilizing existing refining infrastructure.

Fast Pyrolysis Oil

Crude Oil

Co-FCC Route

Feedstock VGO

90% VGO +

10% Bio-oil

80% VGO +

20% Bio-oil

CO 0.1 1.9 3.1

CO20.1 0.5 0.8

Water 0.0 2.3 7.3

Dry Gas 3.9 2.8 2.5

LPG (C3-C4) 15.2 12.9 9.9

Gasoline (C5-220°C)

40.4 40.7 37.7

Diesel (220-344°C)

18.1 17.4 16.5

Bottoms (+ 344°C)

14.8 14.0 13.7

Coke 7.4 7.5 8.5

Can we do better ?

Your logo


35

66 68 70 72 74

37

38

39

40

41

42

43

Ga

so

line

(w

t.%

)

Conversion (wt.%)

Pure VGO

SPO-2 co-cracking

SPO-1 co-cracking

PL co-cracking

(c)

VGO + 10% PL

VGO + 10% SPO

pure VGO

Wang et al. 2018, Fuel Processing technology, accepted for publication

SPO-1

SPO-2

Your logo


optimize HDO conditions, viz. minimise H2 consumption reduce CO2 production

• Higher OPEX / CAPEX• Reduction of carbon efficiency• H2 consumption

• Improves liquid quality• Water content lower

Impact on HDO Impact on FCC• Cost of feedstock

• Improves processability• Better selectivity• Less catalysts deactivation• Higher C-yield to liquids

Up-grading by hydrogenation / hydrodeoxygenation

Your logo

Fast pyrolysis: take home messages

• Fast pyrolysis has become mature

• Pyrolysis seems one of the cheapest options to produce 2G biofuels especially if integrated in existing refineries

• Pyrolysis is a pretreatment of biomass to (petro)refineries, and to solve biomass logistics (turn it in a liquid) –

what about IH² and HTL ?

• Short term: Need to demonstrate biomass to fuels by co-FCC of pure PL

• Longer term: To increase carbon efficiency by co-FCC treated PL (SPO)

• What is needed ?

• Make pyrolysis liquids a commodity

• Reduce costs feedstocks (residual materials)

• Better catalysts for stabilization (from 200 to 5000 kg PL/kg cat)

• Better processes for stabilization, more data on co-FCC in bench scale unit

• Chemical engineers to transform these liquids into something better

Your logo

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 764089

Prof. dr. ir. Frederik Ronsse

Dr. Robbie VenderboschBTG

Josink Esweg 34

7545 PN, EnschedeThe Netherlands

Additional acknowledgements to the following EU projects:

fast pyrolysis and hydrothermal processing · 2019-11-08 · your logo this project has received...

Documents