Tech focus: Hydrothermal liquefaction of low-value biomass for marine, land

and aviation transport  

Saqib  Sohail  Toor,  PhD  Assistant  Professor  Department  of  Energy  Technology,  Aalborg  University,  Denmark  27th  June,  2012  

1/17  

Advanced  Biofuel  Workshop  

Current status of world energy

Liquid biofuels

Hydrothermal liquefaction

Bio-fuel lab at IET

Biofuel for marine, land and aviation transport

•  for marine

•  for land

•  for aviation

From biomass to transportation fuels and chemicals, the co-processing concept

Current status of world energy

World energy consumption by fuel, 1990‑2035 (quadrillion Btu)

Source: International Energy Outlook (2011)

•  Liquids consumption increases at an average annual rate of 1.0 percent from 2008 to 2035.

•  Total energy demand increases by 1.6 percent per year.

•  Renewables are the fastest-growing source of world energy, with consumption increasing by 2.8 percent per year.

World liquids consumption by sector, 2008‑2035 (million barrels per day)

•  Transportation share of total liquid fuels consumption increases, accounting for about 80 percent of the overall increase in liquids consumption in all sectors over the projection period.

•  In 2035, the transportation sector consumes 60 percent of total liquids supplied, as compared with 54 percent in 2008.

Liquid biofuels

First Generation (from sugars, grains, or seeds) • Biodiesel (fatty acid methyl ester; fatty acid ethyl ester) – rapeseed (RME), soybeans (SME), sunflowers, jatropha, coconut, palm, recycled cooking oil • Bioethanol – From grains or seeds: corn, wheat, potato – From sugar crops: sugar beets, sugarcane Second Generation (from lignocellulose and wastes: crop residues, grasses, woody crops, algae, manure, and sewage sludge) • Ethanol via enzymatic hydrolysis • Thermochemical fuels – Fischer-Tropsch liquids (FTL) – Methanol, MTBE, gasoline – Dimethyl ether (DME) – Mixed alcohols – Hydrothermal liquefaction – Pyrolysis oils

via  gasifica,on  

Use of sugar or starch crops:

•  Competition for food uses.

•  Plants optimized for food, not energy.

•  Only part of the plant is converted to biofuel.

•  Limited large-scale experience outside Brazil and USA.

•  Relatively high costs (except sugarcane ethanol in Brazil) due to high feedstock cost.

Use of lignocellulosic materials:

•  These are generally not edible.

•  Plants can be bred for energy characteristics.

•  Larger fraction of the plant is converted to fuel.

•  Biorefinery maximizes plant utilization.

Hydrothermal Liquefaction

•  Operates in the range of 280-370 oC and 10-25 MPa. •  Suitable for wet biomass, directly converted without an energy consuming drying step like in gasification&pyrolysis. •  Product oil has lower oxygen content than pyrolysis oil and also a better chemical stability. •  The upgraded oil can be co-processed with fossil feed to obtain a product that can be readily incorporated in the refinery process chain.

Toor, S.S., Rosendahl, L.A., Rudolf, A., 2011. Hydrothermal liquefaction of biomass: A review of sub-critical water technologies. Energy, Vol. 36, Issue 5, P 2328-2342.

Hydrothermal liquefaction

Water soluble organic fraction

Raw bio-oil (unrefined)

Upgraded bio-oil

Gaseous product mainly CO2

Liquefaction product

Effect of catalysts

•  Increase liquid yields

•  Depends on the catalyst, kind of feedstock, and reaction time

Table 1. Overview of hydrothermal liquefaction processes in pilot or demonstration scale

Process Name Developer/Supplier of the Process

Raw Material Liquefaction (T), oC

Liquefaction (P), MPa

Plant Scale Oil yield (%)

PERC-Process Pittsburg Energy Research Center (USA)

Wood Chips 330-370 20 N/A 53

LBL-Process Lawrence Berkeley Laboratory (USA)

Wood Chips 330-360 10-24 N/A 33

HTU-Process Shell Research Institute (NL)

All types of biomass, domestic, agricultural, and industrial residues, wood

300-350 12-18 100 kg/h (wet) pilot plant

Not known

DoS-Process HAW (GER) Lignocellulosic biomass (e.g. wood, straw)

350-500 8.0 5 kg/h semicontinuous test plant

Not known

STORS process, USA

EPA’s Water Engineering Research Laboratory, Cincinnati, Ohio, USA

Sewage sludge 300 Not known 30 kg of sludge per hour

Not known

STORS process, Japan

Organo Corp. Sewage sludge 300 10 5 tones of sludge per day

38

CatLiq®-Process

SCF Technologies A/S (DK)

DDGS 280-350 22.5-25 20 L/h capacity pilot plant

34

Thermal Conversion Process (TDP)

Changing World Technologies Inc. (USA)

Turkey offal and fats 200-300 4.0 250 tons/day Not known

Toor, S.S., Rosendahl, L.A., Rudolf, A., 2011. Hydrothermal liquefaction of biomass: A review of sub-critical water technologies. Energy, Vol. 36, Issue 5, P 2328-2342.

Bio-fuel lab at IET

•  400ml batch reactor system •  Max. working temp.= 500 oC •  Max. working pressure = 350 bar

Sewage  sludge  (Biological)  Aalborg  Vest  plant  

Sewage  sludge  (Primary)  Aalborg  Vest  plant  

Manure  

Manure  (Slurry)  

DDGS  (Grinded) Corn  Silage

Algae  (Chlorella)  

Algae  (Spirulina)

Biomass C H N S O Dried Distillers Grains with Solubles (DDGS)

43.48 5.88 5.02 1.06 44.56

Corn silage

43.31

5.50

2.66

0.47

48.06

Chlorella vulgaris 45.14 6.16 7.60 0.99 40.11 Spirulina platensis

42.26

5.86

3.47

1.15

47.26

Primary sewage sludge

44.92

6.31

10.41

1.15

37.21

Biological sewage sludge

32.30

5.18

6.11

0.94

55.47

Pig manure

42.72

5.27

1.56

0.63

49.82

Pig manure slurry

37.60

5.21

2.98

1.04

53.17

Ultimate analysis of various biomass (wt%).

Biomass Moisture Ash Volatile matter

Fixed carbon Calorific value (MJ/Kg)

Dried Distillers Grains with Solubles (DDGS)

7.68 5.86 87.24 6.90 19.136

Corn silage

5.60

7.78

88.38

3.85

17.378

Chlorella vulgaris 6.00 7.53 87.27 5.19 19.851 Spirulina platensis

5.88

9.01

86.84

4.15

20.396

Primary sewage sludge

4.97

19.46

77.33

3.20

18.997

Biological sewage sludge

11.38

40.16

53.70

6.14

15.689

Pig manure

5.11

13.28

85.50

1.22

17.440

Pig manure slurry

10.28

26.02

70.81

3.17

16.954

Proximate analysis (wt%) and Calorific value of various biomass

The composition of the DDGS used in the experiments

Over-all results of the experiments, values are given with 95% confidence intervals

Properties of the bio-oil, representative sample

Elementary composition, daf *(wt %)

C 45.50

H 7.0

N 8.10

S 0.79

O 38.7

Major components wt%

Protein 35

Moisture 6.0

Fibers 47

Fat 5.5

Ash contents (db) 4.0

Starch 1.7

Oil yield on dry biomass (%)

33.9 ± 1.8

Energy recovery in oil (%) 73.2 ± 3.9

Carbon recovery from biomass to oil (%)

57.8 ± 2.8

Low heat value of oil* (MJ/kg) 35.8 ± 0.2

Elementary composition of oil (%)

C 78.3 ± 0.3

H 9.3 ± 0.1

O 5.1 ± 0.4

N 6.4± 0.4

S 0.4± 0.1

Viscosity at 40 oC, (cP)

499 ± 52

Viscosity at 60 oC, (cP) 116 ± 10

Viscosity at 80 oC, (cP) 39 ± 3

Water content in oil (%) 7.2 ± 0.9

Ash content in oil (%)* 0.6 ± 0.1

*daf, dry ash free

* corrected for the water content

* Water-free

Toor, S.S., Rosendahl, L.A., Nielsen, M.P., Glasius, M., Rudolf, A., Iversen, S.B., 2012. Continuous production of bio-oil by catalytic liquefaction from wet distiller’s grain with soluble (WDGS) from bio-ethanol production. Biomass and Bioenergy, Vol. 36, P 327-332.

Experiment with DDGS (Dried distillers grains with solubles):

Compound Quantity (mg/L)

Methanol 252

Ethanol 290

1-Propanol 40

Butanol 40

Acetone 110

Acetic acid 3320

Propionic acid 727

Butanic acid 305

Valeric acid 230

Isovaleric acid 241.23

Gas Phase Analysis: The gas contained about 95% CO2 and 1.6% H2, small amounts of N2, CO and CH4 as well as traces of short-chain alkanes and alkenes.

Concentration of short-chained alcohols and acids in water phase

Raw  Material

Liquefac,on  products

Water  solu,on Water  insoluble  frac,on

Acetone  solu,on Acetone  insoluble  frac,on

Heavy  oil Residue   Water  soluble  frac,on  (Organics  Dissolved) Gases  products

Liquefac,on  

Filtra,on    

Evapora,on   Drying    

Extrac,ng  with  acetone   Filtra,on    

Experiment with algae:

•  25% dry matter •  water as a solvent •  without catalyst •  10-30 min residence time

Composi,on     Average  %  Protein   60  Carbohydrates   19  Fats   6  Minerals   8  Moisture     7  

Spirulina platensis composition by supplier

Spirulina platensis

Nannochloropsis salina (USA)

Spirulina platensis  

T=180-310 oC P=100-120 bar t =10-30 min.  

T=330-350 oC, P=150-200 bar, t = 10-30 min.  

T=360-375 oC P=225-250 bar t = 10-30 min.  

Bio-oil (g)   15   19   19  Oil yield (%)   30%   38%   38%  

Nannochloropsis salina (USA) Bio-oil (g)   23   17   -  

Oil yield (%)   46%   34%   -  

Products from spirulina

Products from salina

Oil+water+solid

Biofuel for marine, land and aviation transport

Source: IEA, 2010c

IEA biofuels roadmap April 2011, Use of biofuels in different transport modes in 2050

Biofuels for marine

Future challenges: •  Strict world wide requirements on sulphur from 2020 (2025) •  CO2 emissions from shipping •  2015: vessels operating in ECA areas must burn sulphur max 0.1% Relative CO2 targets from Maersk Business Units: • Maersk Line 25% reduction per TEU-km from 2007 to 2020 Maersk Line wants as part of its sustainability strategy to test potential biofuels and explore the opportunities for developing biofuels tailor made for shipping. • Maersk Tankers 15% reduction per tonne-km from 2007 to 2015 Maersk Line see biofuel as part of the future CO2 and sulphur reduction strategy.

Elementary composition of oil (%)

C 78.3 ± 0.3

H 9.3 ± 0.1

O 5.1 ± 0.4

N 6.4± 0.4

S 0.4± 0.1

DDGS bio-oil analysis

Source: Biofuel Network Conference, Copenhagen, April 28th, 2011, Maersk Maritime Technology Perry’s Chemical Engineer’s Handbook, 7th Edition

Biofuels and shipping - challenges

• Price competitiveness – need for “low-grade” fuels.

• Storage stability of products.

• No major focus on shipping in biofuel industry.

• Need for firm implemented sustainability criteria.

• Quantities and infrastructure needed.

• Food vs. Feed.

• APMM will not use fuels competing with feed.

What bio derived oils can be applied as marine bunker?

•  Secure the bio product intended to be applied as bunker fuel , comply with ISO 8217:2010.

•  Bio fuel to be delivered has to be low on acids – ISO limit for Acid Number (ASTM D664) max 0.5%.

•  The specific type of bio fuel has to be suitable as marine fuel and compatible/miscible with other marine fuels.

•  Biofuels has to be derived from a sustainable carbon source.

Biofuels for land

Popular biofuels (blends) Within fuel specification

“gasoline replacement”: •  Ethanol: low blend in standard vehicles •  Ethanol: high blend in FFV •  Biogas (upgraded to NG quality)

0 -10% 0 - 85% 0 - 100%

“diesel replacement”: •  Biodiesel: methyl esters: FAME. FAEE •  HVO: Hydrotreatment Vegetable Oil •  BTL: Biomass to Liquid

0 - 7 % 0 - 30% 0 - 30%

Biodiesel (FAME) can seriously affect the performance and durability of emission control systems:

• Injector deposits, valve sticking, catalyst poisoning, Increases NOx

•  Bio ethanol is presently limited to low-concentration blends (5–10% by volume), namely E5–E10.

•  High-concentration blends, can cause corrosion of some metallic components in tanks and deterioration of rubbers and plastics used in

internal combustion engines.

•  Less energy per volume (energy density) than conventional gasoline, which ultimately reduces the fuel mileage of the vehicles.

•  Conventional transportation fuels are composed of liquid hydrocarbons with different molecular weights (e.g., C5–C12 for gasoline, C9–C16 for jet fuel, and C10–C20 for diesel applications) and chemical structures (e.g., branched for gasoline, linear for diesel).

•  The entire transportation infrastructure (including engines, fueling stations, distribution networks, and storage tanks) has been developed to take advantage of the excellent properties of these compounds as fuels. •  Instead of using biomass to produce oxygenated fuels, an attractive alternative would be to utilize biomass to generate liquid fuels chemically similar to those being used today derived from oil.

Why HTL fuel:

Some facts about Bioethanol:

Source: http://www.iata.org/pressroom/facts_figures/fact_sheets/Pages/alt-fuels.aspx

Biofuels for aviation

Main requirements for sustainable alternative jet fuels: •  Can be mixed with conventional jet fuel, can use the same supply infrastructure?

•  Meet the same specifications as conventional jet fuel (min 42.8 MJ/kg).

•  Meet sustainability criteria, such as lifecycle carbon reductions, no competition with fresh water requirements or food production.

•  Automotive bioethanol and biodiesel are not suitable.

Sustainable aviation biofuels (“biojet fuels”) are one of the most promising solutions to meet IATA’s high-level carbon emissions

reduction goals. Sustainable Sources of Biomass: Biofuels should be made from sustainable, non-food biomass sources such as algae, jatropha, switch grass as well as municipal waste.

•  Algae are simple, photosynthetic organisms. •  Can be grown with polluted or salt water. •  Can produce up to 250 times more oil than first generation soybeans.

Soybean feedstock would be unable to meet aviation fuel demand

Algae might be able to meet aviation’s fuel demand

Jet Fuels in Practice: Between 2008 and 2011, nine airlines and several aircraft manufacturers performed flight tests with various blends of up to 50% biojet fuel. These tests demonstrated that the use of biojet from these sources as ‘drop-in’ fuels is technically sound. Airlines involved: KLM, Lufthansa, Finnair, Interjet, Aeroméxico, Iberia, Thomson Airways, Air France, United, Air China, Alaska Airlines, Thai Airways, LAN, Qantas, Jetstar. Certification: •  IATA is working with industry partners toward agreed-upon production standards and test and certification requirements.

•  In 2009 the fuel certifying body ASTM International approved a new specification enabling the use of synthetic (Fischer-Tropsch) fuel

blends, such as BTL (Biomass to Liquid), up to 50% in aviation (ASTM D7566).

•  It is expected that by 2013, two additional alternative fuels will be added to ASTM D7566: alcohol to jet (ATJ) and synthetic kerosene

containing aromatics (SKA).

Source: http://www.iata.org/pressroom/facts_figures/fact_sheets/Pages/alt-fuels.aspx

IATA’s Strategic Action Plan Industry actions: •  Attract investors to build up biojet fuel production facilities •  Build demonstration plants as a first step of large-scale industrial deployment •  Synergies with automotive biofuel production •  Scale up capacity Role of governments: •  Globally agreed sustainability standards •  Public incentives for aviation biofuel production and use •  Support biojet R&D and demonstration plants •  De-risking of investments into biojet production plants •  Public / Private Partnerships for biojet fuel production

From biomass to transportation fuels and chemicals, the co-processing concept

A route should consists of the use of decentralised HTL units (located where biomass is available) and transportation of the resulting HTL oil to a central upgrading plant. This plant should be located close to a standard refinery.

The main advantages of this route are:

1.  The upgrading plant can be located next or inside the (existing) refinery. In this way, the required process utilities and product distribution network are already available, creating a product compatible with existing end user requirements.

2.  Using this concept, it is neither necessary to build a whole new bio-refinery nor to invest in new re-fuelling stations or car engines.

Standard  refinery HTL  plant

HTL  plant HTL  plant HTL  plant

HTL  oil

Upgrading  plant

Transporta,on  fuels Chemicals   Heat  and  power  

Biomass   Biomass   Biomass  

Biomass  

Thank You!