DLR.de • Chart 1 R.- SUMMER SCHOOL 2019

Advanced Biorefinery Concepts Towards Certified Jet Fuel

Sandra Adelung, Ralph-Uwe Dietrich, Stefan Estelmann, Simon Maier,

Julia Weyand

ABC-Salt Summer School 2019

Birmingham, 14.08.2019

DLR.de • Chart 1 R.-U. Dietrich • Advanced Biorefinery concepts Towards Certified Jet Fuel • Aston, UK • 14.08.2019

SUMMER SCHOOL 2019ABC-Salt project has received funding from the EU’s Horizon 2020

research and innovation Programme under Grant Agreement No 764089

SUMMER SCHOOL 2019

Agenda

A. Introduction

B. Biomass-to-Liquid: Routes and Unit Operations

→ Feedstock, conversion and conditioning, synthesis, refining

C. Methodology for assessing different routes

→ Technical, economic, ecologic

D. Take-home-messages

R.-U. Dietrich • Advanced Biorefinery concepts Towards Certified Jet Fuel • Aston, UK • 14.08.2019DLR.de • Chart 2

SUMMER SCHOOL 2019

Definition: Biorefinery

IEA Bioenergy Task 42:

“Biorefinery is the sustainable processing of biomass into a spectrum of

marketable products and energy. “

→ Biorefineries can be facilities, processes, plants or cluster of facilities


Biomass Biorefinery

Fuels

Chemicals

Power

Heat

…

Biorefinery

SUMMER SCHOOL 2019

Biorefineries- Classification (IEA Bioenergy Task 42)


Feedstocks

Energy cropsStarch crops, oil crops, sugar crops, …

Biomass residuesStraw, bark, cooking oils, …

Products

EnergyBio-ethanol, biodiesel, FT-fuels, …

ProductsChemicals, materials, …

Platforms / Intermediates

C5/C6, sugars, syngas, biogas, …

Conversion processes

Biochemical(fermentation, enzymatic conv., …)

Thermochemical(gasification, pyrolysis, …)

Chemical(acidic hydrolysis, esterification, …)

Mechanical(fractionation, milling, …)

Multiple process routes

possible

SUMMER SCHOOL 2019

Biomass-to-Fuels


SUMMER SCHOOL 2019DLR.de • Chart 6DLR.de • Chart 6

EU 28 bioenergy potential[1]

DLR.de • Chart 6 R.-U. Dietrich • Biorefineries concepts and design • ABC-Salt Summer School • 14.08.2019

Feedstock Biomass category Biomass type PJ (2020)

Agriculture

Energy crops1 Sugar, oil crops, starchy crops, lignocellulosic biomass, energy maize

3,184

Agricultural residues

Dry & liquid manure, straw, olive pits 2,312

Forestry

Stem wood production

Stem wood, woodchips 2,096

Forestry residuesLogging residues, landscape care, woodchips, saw dust, black liquor

3,166

Waste Residues Public greens, solid waste, sewage sludge 454

[1] Pablo Ruiz et al.. (2015): „The JRC-EU-TIMES model. Bioenergy potentials for EU and neighbouring countries.”, JRC Science for policy report

[2] Carolina Perpiña Castillo et al. (2015): An assessment of dedicated energy crops in Europe under the EU Energy Reference Scenario 2013, JRC Science for policy report

1Land use of energy crops in 2020: 4,733 kha (1.3 % of total available land , ~2.4 % of agricultural land)[2]

R.-U. Dietrich • Advanced Biorefinery concepts Towards Certified Jet Fuel • Aston, UK • 14.08.2019

SUMMER SCHOOL 2019

EU 28 bioenergy potential-2010[1] – regional distribution


[1] Pablo Ruiz et al.. (2015): „The JRC-EU-TIMES model. Bioenergy potentials for EU and neighbouring countries.”, JRC Science for policy report

Highest potential:

France, Germany,

Spain, Poland,

Sweden, Italy,

Romania

SUMMER SCHOOL 2019

Certified alternative jet fuels (ASTM D7566 – 14c [1])


Feedstock Synthesis technology Fuel

Coal, natural gas, biomass, CO2 & H2 Fischer-Tropsch (FT) synthesis Synthetic paraffinic kerosene

(SPK)

Lipids from Biomass (e.g. algae, soya, jatropha) Hydroprocessed esters and fatty acids (HEFA) Synthetic paraffinic kerosene

Sugar from Biomass Direct Sugars to Hydrocarbons (DSHC) Synthetic iso-paraffins /

Farnesane

Bioethanol (-propanol, -butanol) dehydration+oligomerization+hydration

(Alcohol-to-Jet, AtJ)

AD-SPK

[1] ASTM International, „ASTM D7566 - 14C: Standard Specification for Aviation Turbine Fuel Containing Synthesized Hydrocarbons“, 2015

[2] Dietrich et al., “Challenges & opportunities for sustainable aviation”, 13th Concawe Symposium - Low Carbon Pathways and Refining Technologies, March 2019, Antwerp

European crop based kerosene? – from rapeseed & soya / sugar beet / wheat

All European rapeseed & soya to HEFA: 14.7 Mt/a (≈ 26 % of aviation demand) [2]

All European sugar beet to DSHC: 3.4 Mt/a (≈ 6 % of demand) [2]

All European wheat to AtJ: 31.9 Mt/a (≈ 56 % of demand) [2]

SUMMER SCHOOL 2019

Certified alternative jet fuels (ASTM D7566 – 14c [1])


Feedstock Synthesis technology Fuel

Coal, natural gas, biomass, CO2 & H2 Fischer-Tropsch (FT) synthesis Synthetic paraffinic kerosene

(SPK)

Lipids from Biomass (e.g. algae, soya, jatropha) Hydroprocessed esters and fatty acids (HEFA) Synthetic paraffinic kerosene

Sugar from Biomass Direct Sugars to Hydrocarbons (DSHC) Synthetic iso-paraffins /

Farnesane

Bioethanol (-propanol, -butanol) dehydration+oligomerization+hydration

(Alcohol-to-Jet, AtJ)

AD-SPK


[2] Pablo Ruiz, „The JRC-EU-TIMES model. Bioenergy potentials for EU and neighbouring countries”, Table 38-43, 2015

[3] Albrecht, “A standardized methodology for the techno-economic evaluation of alternaitve fuels – a case study”, 2016

European BtL Fischer-Tropsch kerosene? – from forestry and municipal waste:

Forest residues, municipal waste potential [2]: ≈ 8 EJLHV/a

Conversion to fuel[ 3]: 0.363 PLHV,Kerosene/PLHV,Biomass

European kerosene production based on BtL: 68.4 Mt/a (121 % of aviation demand)

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Biomass-to-Fuels


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Gasification - Types


Moving bed Fluidized bed Entrained flow

Fuel feeding Dry Dry Dry/Slurry

Typical process Lurgi, BGL Winkler, HTW, HRL, CFB, KBR, KRW, U-Gas

KT, Shell, Siemens, EAGLE, GEE, E-Gas, ICCT OMB

Fuel size limits 5 – 80 mm < 6 mm < 0.1 mm

Oper. Temperature ~ 1000 °C 800 – 1100 °C > 1200 °C

Oper. Pressure > 20 bar 1 – 35 bar 1 – 85 bar

Oxidant demand Low Moderate High

Product gas temperature 400 – 650 °C 900 – 1050 °C 1250 – 1600 °C

SUMMER SCHOOL 2019

Pyrolysis- Products[1]

Different operating conditions:

• Residence time

• Temperature

• Heating rate

→ varying product compositions

→ post-processing varies


[1] John A. Dutton e-Education Institute: “Alternative Fuels from Biomass sources”, https://www.e-education.psu.edu/egee439/node/537

SUMMER SCHOOL 2019

Pyrolysis- Products[1]


[1] John A. Dutton e-Education Institute: “Alternative Fuels from Biomass sources”, https://www.e-education.psu.edu/egee439/node/537

• Consists of about 400 types of organic

compounds (Acids, Esters, Alcohols,

Ketones, Aldehydes, Phenols,

Alkenes, Aromatics, …)

-> high value components?

• Immiscible with transportation fuels

but emulsifying with Diesel possible

-> special surfactants

• Water content emulsified

-> separation problem

ABC-Salt

Approach

– Bio-Oil properties

SUMMER SCHOOL 2019

Pre-Treatment and hydrolysis

Pre-Treatment possibilities

• Milling

• Drying

• Acidic

• Alkaline

• Solvents

• Oxidants


Pre-treatment

(Physical, thermo-chemical)

Enzymatic Hydrolysis Acidic Hydrolysis

Sugars

Biomass

SUMMER SCHOOL 2019

Biomass-to-Fuels


SUMMER SCHOOL 2019

Synthesis from Syngas


Fischer-Tropsch MeOH EtOH

ProductMostly alkanes or alkenes

(product distribution α = 0.75-0.95)Methanol

Ethanol and higher

alcohols

TemperatureLTFT (190 – 250°C)

HTFT (300 – 350°C)200-300 °C 200-300 °C

Pressure 25-40 bar 40-150 bar 40-100 bar

Reactor

typesSlurry, Fixed-bed, micro-channel Fixed-bed Fixed-bed

Feed H2/CO = 2.0-2.2 H2/(2CO + 3CO2) = 1.05 H2/CO = 0.45-2.33

TRL 8-9 8-9 1-3

SUMMER SCHOOL 2019

Synthesis from Sugars


Fermentation Aqueous phase reforming

Product EthanolFarnesane

(kerosene blend)Alkanes, alkenes and oxygenates

Temperature 32 - 34 °C 180 – 370 °C

Pressure Ambient 10 - 90 bar

Environment Anaerobic Aerobic -

Feed Mono-saccharidesPolyhydric alcohols,

short-chain oxygenates

SUMMER SCHOOL 2019

Biomass-to-Fuels


SUMMER SCHOOL 2019

Refining unit operations

• Hydrocracking

• Decrease chain length

• Dehydrogenation/Hydrogenation

• Remove/add hydrogen from molecules →

increase alkene/alkane content

• Dehydration/ Hydration

• Decrease/increase alcohol content


+H2

→ 2

⇌+H2

-H2

OH+ H2O

+H2

-H2

⇌

SUMMER SCHOOL 2019

Refining unit operations – cont.

• Alkylation

• Merge aliphatic HCs/aromatics with alkenes

(increase octane number, RON)

• Oligomerization

• Increase chain length of alkenes

(increase boiling point, energy density)

• Isomerization (alkenes)/ Hydroisomerization (alkanes)

• Increase number of branches, RON

• De-/Aromatization

• De-/Increase number of aromatics

(Reduce soot formation / increase RON)


+ →

⇌

2 ⇌

⇌-H2

+H2

SUMMER SCHOOL 2019

Refining design objectives and design hierarchy


Feed Characterization

Product specification

Conversion processes

Separation processes

Heat integration

Utilities

• Primary Design Objectives

• Refinery type

• Products and markets

• Feed selection

• Location

• Secondary Design Objectives

• NPC ↓

• CAPEX ↓

• Efficicency ↑

• Environmental footprint ↓

• Flexibility ↑

• Complexity ↓

• …

SUMMER SCHOOL 2019

Biomass-to-Fuels


SUMMER SCHOOL 2019

Transportation fuels specifications - Gasoline and Diesel


RON

MON

AromaticsOlefines

SulfurBoiling Point

Vapour pressureDensity

C5+ ethers

C3+ alcohols

EthanolMethanol

Benzene

Cetane number

Flash point

Lubricity

Unwashed gums

Washed gums

Gasoline

Polycyclic aromatics

Water

Distillation points

Region specific: US, EU + Time dependent: Euro-5, Euro-6, …

Diesel

SUMMER SCHOOL 2019

Selected specifications for Jet A-1 from Fischer-Tropsch synthesis


Property Up to 50 % Blend [1]

Net heat of combustion

[MJ/kg]min. 42,8

Density at 15 °C [kg/m3] 775-840

Viscosity at -20 °C [mm2/s] max. 8000

Freezing point [°C] max. -47

Flash point [°C] min. 38

Aromatics [Vol. %] max. 25

Distillation:

T10-TFinal[°C] 205 - 300


Jet A-1 from FT-synthesis:

• Drop-in fuel

(ASTM D7566 – 14c [1])

• Fully synthetic (100 %) certified

by Royal Airforce (U.K.)

SUMMER SCHOOL 2019

Techno-Economic and ecological assessment (TEEA)


Alternative jet fuel

Technical evaluation

Ecological evaluation

Economic assessment

DLR’s Techno economic

process evaluation tool

Efficiencies (X-to-Liquid, Overall)

Carbon conversion

Specific feedstock demand

Exergy analysis

CAPEX, OPEX, NPC

Sensitivity analysis

Identification of most economic

feasible process design GHG-footprint

GHG-abatement costs

SUMMER SCHOOL 2019

Techno-economic assessment

DLR Methodology


Literature

survey

1. Step

Identification of best

suited process design

Energy and material

balance

3. Step 4. Step

Identifying

crucial

process

parameters

Feedback to

project

partners

5. Step

Exchange

with project

partners

2. Step

Detailed

process

simulation

Stationary flowsheet

model

Technical

optimization (Process

control,

Heat integration, …)

Techno-

economic

evaluation

TEPET-

ASPEN Link

Exchange of process

parameters

Automatic sequencing

and economic

optimization

Calculation of NPC

(CAPEX, OPEX, etc.)

Sensitivity analysis &

upscaling

Iteration

Aspen Plus®

Simulation

SUMMER SCHOOL 2019

Process scheme (block flow diagram)

Example: EU-Project COMSYN


COMSYN project has received funding

from the European Union’s Horizon 2020

research and innovation programme

under grant agreement No 727476

SUMMER SCHOOL 2019

Second step: AspenPlus flowsheet model

Example: EU-Project COMSYN


Drying and

Gasification sectionReforming and

gas cleaning section

FT-Synthesis

sectionCentralized product

upgrading section





Design data of each unit required

SUMMER SCHOOL 2019

AspenPlus – Heat integration

Process flowsheet – Heat integration






SUMMER SCHOOL 2019

0

100

200

300

400

500

600

700

800

900

1000

0 20 40 60 80 100 120

Tem

pera

ture

/ °

C

Energy / MW

Warm Stream Cold Stream

AspenPlus – Technical assessment

Example – Heat integration – Composite curves


High amount of

excess heat > 400 °C

cooling demand

(< 90 °C)

SUMMER SCHOOL 2019






Economic assessment



CAPEX, OPEX, NPC

Sensitivity analysis

Identification of most economic

feasible process design

SUMMER SCHOOL 2019

TEPET – Economic assessment

Methodology


Plant and unit sizes

Capital costs

• Equipment costs

• Piping & installation

• Factory buildings

• Engineering services …

Process simulation

results

SUMMER SCHOOL 2019


Methodology



Process simulation

results

Equipment costs:

• Standard equipment (compressors, pumps, heat exchangers):Chemical engineering data for industrial plants [1]

• Non-standard equipment (reactors, electrolyzers):Literature survey/Exchange with project partnersABC-Salt: project partners best guess?

[1] Peters M., Timmerhaus K., West R., Plant design and economics for chemical engineers, 2004

Capital costs

• Equipment costs




SUMMER SCHOOL 2019


Methodology



Material and energy balance

Operational costs

• Raw materials

• Operating materials

• Maintenance

• Labor costs …

Process simulation

results

Capital costs

• Equipment costs




SUMMER SCHOOL 2019


Methodology


Capital costs

• Equipment costs







Operational costs

• Raw materials


• Maintenance

• Wages …

Process simulation

results

• Raw material prices and by-product revenues are year-specific (2017) introduced for Germany (stock market, market surveys)ABC-Salt: Different markets?

• Labor costs based on German labor market

Operational costs

• Raw materials


• Maintenance

• Labor costs …

SUMMER SCHOOL 2019


Methodology




Net production costs

(NPC) [€/l; €/kg; €/MJ]

Capital costs

• Equipment costs




Process simulation

results

Operational costs

• Raw materials


• Maintenance

• Labor costs …

SUMMER SCHOOL 2019

-0.5

0

0.5

1

1.5

2

2.5

3

3.5

Pro

du

ctio

n c

ost

s in

€/l

Electrolyzer

Fischer-Tropsch synthesis

Gasifier

Rest (CAPEX)

Biomass

Electricity

Oxygen

Remaining (Raw materials & Utilities)

Revenue from by-products

Maintenance

Labor costs

Rest (OPEX)

Example: TEEA of sustainable Jet fuel production

Base year: 2017


• 100 MWth biomass feed

• Annual production: 24.2 kt/a

• 2.86 €/liter FT-product

• Investment costs: 510 m€

• 100 MWth biomass feed

• + 164 MWe electrical power

• Annual production: 91.3 kt/a

• 2.51 €/liter FT-product

• Investment costs: 990 m€

SUMMER SCHOOL 2019






Economic assessment



GHG-footprint

GHG-abatement costs

SUMMER SCHOOL 2019

GHG abatement costs

Example: Fischer-Tropsch jet fuel GHG Footprint


Electricity GHG

Footprint

GHG Footprint of

products

𝐆𝐇𝐆 𝐚𝐛𝐚𝐭𝐞𝐦𝐞𝐧𝐭 𝐜𝐨𝐬𝐭𝐬€

𝐭𝐂𝐎𝟐𝐞𝐪.=

𝐃𝐢𝐟𝐟𝐞𝐫𝐞𝐧𝐜𝐞 𝐢𝐧 𝐩𝐫𝐨𝐝𝐮𝐜𝐭𝐢𝐨𝐧 𝐜𝐨𝐬𝐭𝐬

𝐆𝐇𝐆 𝐚𝐛𝐚𝐭𝐞𝐦𝐞𝐧𝐭

Biorefinery

• System integration

• Efficiency

• Plant emissions

• Crediting of by-products

(steam, electricity, …)

Biomass GHG

footprint

Application

efficiency

SUMMER SCHOOL 2019

Take-home-messages

• Biomass residues could (theoretically) cover the foreseen European kerosene demand

→ Utilization competition

• No “Silver Bullet” Biomass-to-Liquid process route

→ Biochemical, thermochemical, chemical, mechanical conversion processes have to be adapted to

varying feedstock and product compositions

→ Refining and upgrading requires multiple unit operations to meet different product specifications

• Assessment requires transparency, reliability, accuracy → and collaboration

→ Techno-economic and ecologic evaluation methodology available for biorefinery concept comparison


Thank you for your attention!

Sandra Adelung, Ralph-Uwe Dietrich,

Felx Habermeyer, Simon Maier,

Moritz Raab, Julia Weyand


ABC-Salt project has received funding from the EU’s Horizon 2020

research and innovation Programme under Grant Agreement No 764089

SUMMER SCHOOL 2019

DLR.de • Chart 1 R.- SUMMER SCHOOL 2019

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