t

TNO Environment, Energy and Process Innovation

Crude oil from biomass with the HTU® processExample of an Early Stage Technology

Jaap Koppejan

EMIMENT workshop, 8-9 03 2004, Riga

8 March 2004EMINENT 2t

HTU = crude oil from biomass

8 March 2004EMINENT 3t

What is HTU ?Conditions: 300 – 350°C; 120 - 180 bar

reaction time 5 - 20 minutesliquid water

Feedstocks: All types of biomass, domestic, agricultural and industrial residues, woodAlso wet feedstocks, no drying required

Chemistry: Oxygen removed as Carbon Dioxide

Products 45% Biocrude (%w on feedstock, dry basis)25% Gas (> 90% CO2)20% H2O10% dissolved organics (e.g., acetic acid, methanol)

Thermal efficiency: 70 - 90 %

8 March 2004EMINENT 4t

HTU® Product characteristics

Biocrude - Heavy organic liquid- Solidifies at 80 °C- Not miscible with water- Oxygen content 10 - 18 %w- H/C ratio = 1.1- LHV 30 -35 MJ/kg

Applications

Biocrude: (co)combustion in coal- and oil- fired power stations

After hydrogenation: - premium diesel fuel; kerosene- lubrication oils - chemicals feedstock (cracker)

8 March 2004EMINENT 5t

Perspectives for energy from biomass

1990 2040

Energy demand 350 1000

Delivered by:

Fossil fuels 255 480

Renewables 80 >400

Hydropower 20 50

Wind - 70

Solar - 130

BiomassBiomass 6060 >200>200

(Shell scenario)

8 March 2004EMINENT 6t

Global potential for energy from biomass

Energy farming on 109 ha land area @ 15 ton(db)/ha.year

250 EJ/yr

Biomass residues (Forestry, wheat, rice, sugar cane, corn,etc.

70 EJ/yr

8 March 2004EMINENT 7t

Suitable feedstocks for HTU in Europe

• Agricultural / Industrial Residues 200 Million tons/a (db)

(Source: Eurec agency, 1996)

• Short-term niches for HTU:- Olive Oil Industry 3 - 5 Million tons/a

(db)- Organic household waste 26 ktons/a

(db) per (from centralized waste separation) 250,000

inhabitants- Residues from sugar and beer production.

8 March 2004EMINENT 8t

• Agricultural and industrial residues 4,000 Mt/a (db)

(Source: “Renewable Energy; sources for (approx. 70 EJ/a)

fuels and electricity”, 1993)

• Future organic household waste 800 Mt/a (db)

(own tentative estimate)

• Short-term niches for HTU:- Organic household waste- Bagasse (> 100 Mtons/a)- Forestry residues from existing plantations- Coir dust

Suitable feedstocks for HTU worldwide

8 March 2004EMINENT 9t

Development of HTU

1982 – 1988 Process R&D, Shell Laboratory, Amsterdam

1994 – 1997 Technical-Economic evaluation of HTU technology

1997 – 2000 Process development project

2002 – 2004 Final process development

2006 – 2007 First commercial demonstration

2009 HTU diesel commercially available

8 March 2004EMINENT 10t

Technology Development Path( S - curve)

Scientific Base/ Explanatory

ProcessScouting

Techn./Econ.Feasibility

ProcessDevelopment

CommercialPrototype

HTU diesel commercially available

Next S- curve

Improvedscientific base

2006-2007

2004-2005

2000-2002

1983

2008-2009

8 March 2004EMINENT 11t

HTU pilot plant at TNO• Feed 100 kg/h (wet)• Biocrude product 8 kg/h

8 March 2004EMINENT 12t

Block scheme of HTU pilot plant

Biomass

10-20 kg/hr (db)

High pressure pump

Preheater/Reactor 1

Reactor 2 Cooler

Gas /liquid

separator

CO2

Condensor

Pressure reducer

1 barbiocrude/water collection

storage

gases

330 °C

180 bar

storage

Cooler

CO2

8 March 2004EMINENT 13t

Thermal efficiencyDefinition:

th = (HHV of biocrude output) * 100 %

(HHV of feed) + (HHV from external fuel)

For present process design:

th = 55.62 * 100% = 74.9 % 72.98 + 1.3

(Theoretical maximum for this case is 78.6 %)

8 March 2004EMINENT 14t

Upgrading of biocrude by HDO

• Principle of catalytic Hydrodeoxygenation

has been demonstrated

• Upgrading cost compensated by higher

product value

• Diesel fraction has excellent ignition

properties

• Potential applications:• Transport fuel

• Kerosine

• Fuel in high-efficient gas turbine

• Feedstock for chemicals (via ethylene cracker)

• Etc.

8 March 2004EMINENT 15t

HDO process scheme

Biocrude

Hydrogen

HDOreactorsystem

Fractionator

(from HTU)

electricity

NH3, H2S

C1-C4 gas

H2O

Kerosine

Gas oil

>370°C residue

To refininery pool

Air transport

Diesel fuel forRoad transport

Lubricating oil;chemical feedstock

Naphtha

Separatorsection

Recycle gascompressor

8 March 2004EMINENTt

0

1

2

3

4

5

6

7

8

-1 0 1 2 3

Feedstock price, $/GJ

Bio

cru

de

cost

, $/

GJ

First Plant

Coal (2 $/GJ) / Crude Oil (12 $/bbl) Replacement

Future plant

0

+ 40 $ pe

r ton

CO

2 avoid

ed

energy farmingBiomass residues

- 20

+ 20

+ 60

Production costs of biocrude and costs of avoiding one ton of CO2

8 March 2004EMINENT 17t

0

2

4

6

8

10

-2 -1 0 1 2 3

Biomass HTU Feedstock Price, $/GJ

To

tal P

rod

uct C

ost,

$/G

J

First Plant

Premium Diesel, assumed crude oil =25 $/bbl

Future plant

Biomass residues energy farming

Production costs of HTU diesel

8 March 2004EMINENT 18t

HTU® R&D topics

Most essential items:• Pressurizing feedstock• Continuous integrated operation of pilot plant

Important items• Heating – up feedstock• Oil/water separation• Product properties / applications• Effluent treatment

Design data:• Phase equilibria• Physical properties, esp. at reactor/separator

conditions

8 March 2004EMINENT 19t

Process Development

Work in autoclaves, • 10 ml, 1 liter, 2 liter• Testing of feedstocks and process conditions

Continuous pilot plant• capacity 20 kg/hour (dry basis)• commissioning 1 July 1999• first product prepared: 24 November 1999• 24 h run with verge grass feb 2004• 3 weeks run planned march 2004

8 March 2004EMINENT 20t

Results of first development phase

• Pilot plant construction completed• Pilot plant operation: - process principles verified

- most initial problems solved- 200 kg biocrude produced

• Pressurizing of feedstock successfully proven with commercial prototype pump

• Data on thermodynamics and phase equilibria obtained; model operational

• Waste water treatment routes defined• Product: various applications explored• Process design and cost estimation completed• Fundamental research to start: NWO – Japan project.

8 March 2004EMINENT 21t

Commercial HTU demonstration plant

Location: Large new waste incinerator in Amsterdam, synergy for O&M, wastewater treatment, etc.

Input: Roadside grass7 ton/h of feedstock, 3 t/h on dry basis

Output: 1,4 t/h biocrude (incl ash)

Capital investment 17 M€, startup 2006-2007

8 March 2004EMINENT 22t

Commercial HTU plant