methanol, a multi source and multipurpose energy carrier

1

GothenburgNovember 19, 2013

Ingvar LandälvSenior Project ManagerLTU

METHANOL, a Multi Source and Multipurpose Energy Carrier Alternative IEA Bioenergy / IETS:System and IntegrationAspects of Biomass-basedGasification

2

AGENDA

• Turning alkali in the feedstock to an advantage– Why has Chemrec focused Black Liquor so long?

– Is technology ready for commercialization?

– Can the BLG developments be used for other applications?

• Future Energy System Scenarios– The need to look at the total cost of a new energy system

– An example from the marine sector

– An example from the HD vehicle sector

• Summary

11/26/2013

2

3

Today’s commercial Forrest Industry has two main legs

New Value Streams from Residuals & Spent Pulping LiquorsNew Value Streams from Residuals & Spent Pulping Liquors

PulpMill

Forest

Saw-mill

Pulp

WoodProducts

PulpMill

LogsPulp

Wood

RecoveryBoiler

TODAY

4

BLG is a transformative technology converting pulp mills to biorefineries making efficient use

of the third fraction from the forest

New Value Streams from Residuals & Spent Pulping LiquorsNew Value Streams from Residuals & Spent Pulping Liquors

PulpMill

Forest

Saw-mill

Pulp

WoodProducts

PulpMill

LogsPulp

Wood

RecoveryBoiler

Combined Recoveryand Fuel Generation

Fuel

ForestResidual

TOMORROW

5

BL Energy is a large renewable energy source in some areas of the World e.g. Sweden

5

Nr Mill owner, name Nominalcapacity

Currentcapacity

Year of start-up

1 Billerud, Karlsborg 1250 1500 1980

2 SCA, Munksund 600 1965

3 Smurfit Kappa, Lövholmen 1450 1950 1972

4 SCA, Obbola 1000 2007

5 Husum, M-Real 750 1100 1965

6 Husum, M-Real 700 2000 1978

7 Husum, M-Real 1100 1300 1988

8 Domsjö, Domsjö 375 1958

9 Domsjö, Domsjö 375 1964

10 Dynäs, Mondi 915 1978

11 Östrand, SCA 3300 2006

12 Iggesund, Holmen 520 900 1966

13 Iggesund, Holmen 520 900 1967

14 Vallvik, Rottneros 760/1000 1200 1974/1999

15 Korsnäs, Korsnäs 865 1330 1968

16 Korsnäs, Korsnäs 1550 1550 1987

17 Skutskär, StoraEnso 585 650 1967

18 Skutskär, StoraEnso 1900 2800 1976

19 Frövi, Korsnäs 520 1260 1970

20 Skoghall, Stora Enso 2200/(3350) 2005

21 Gruvön, Billerud 2500/(3300) 2000

22 Billingsfors, Munksjö 230 330 1976

23 Bäckhammar, Wermland Paper 570 750 1976

24 Aspa, Munksjö 510 1200 1973

25 Skärblacka, Billerud 1250 1850 1976

26 Värö, Södra 2500 2002

27 Mönsterås, Södra 4000 1996

28 Mörrum, Södra 2000 2260 1995

1

2 3

4

5 68 97

1011

12

1514

1617 18

192320

212224

25

26 27

28

11

13

Approx:5000 MW

Black Liquor

Close to 20 large plants

6

BL Energy is a substantial energy source in some states in the US e.g. Georgia

More than 100 suitable pulp mills In North Americawith 200-400 MW of Black Liquor per plant

6

In the World:approx. 80 000 MW

Black Liquoror

250 – 300 largeplants

7

Some basics about Black Liquor

• Black Liquor is a Liquid– Easy to feed to a pressurized gasifier– Can be atomized to fine droplets– Rapid gasification rates– Stable properties over time

• Black Liquor is an efficient gasification fuel– Full carbon conversion at ~1000 deg C– Virtually no tar formation– Low methane formation

• Black Liquor is available in large quantities– World BL capacity about 660 TWh– Corresponds to production of ~ 10 billion gal gasoline

equivalents per year– Typically 250-300 MW of BL per pulp mill

… making it a very strong candidateas gasification fuel

8

Chemrec technology generates good quality raw syngas with three main process steps: Gasification, Quenching and Cooling

Raw gas

Green liquor

Condensate

Black liquor

GAS COOLER

REACTOR

QUENCH

Boiler feedwater*

LP-steam*

MP-steam*

Weak wash

GASIFICATION

SEPARATIONOF GAS ANDSMELT

PARTICULATE REMOVAL ANDGAS COOLING

Oxygen

Atomisingmedium

Cooling water

OK raw syngas

* Cooling waterin DP1

9

BL to BioDME: Well proven Concept by Chemrec and LTU in the

Pilot Plant in Piteå

DP-1Plant

WGShift

AmineWash

MeOHSynth.

DMESynth.

Distil-lation

ActiveC Abs

BlackLiquor

O2

BioDME

Raw MeOHstorage

OK raw syngas

10

Development Plant for Oxygen-blown high pressure BL gasification

• Located at the SmurfitKappa mill in Piteå, Sweden• Oxygen-blown and operated at 30 bar(g)• Capacity 20 metric tons per day of black liquor sol ids (3 MW(th))• Used for technical development and design verificat ion• Started up 2005 –Now in operation more than 21 000 hours (10/2013).• Raw syngas converted to BioDME since 2011 (about 6 000 h)• Operations: 10 operators in 5 shifts

11

Accumulated BioDME Production is close to 600 tons in October 2013

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duce

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ioD

ME

, ton

B

C

D E

A

F

G

H

A - Authority inspectionB - MaintenanceC - HolidaysD - Repair of ceramicsE - New equipmentF - Catalyst replacement, change of ownerG - MaintenanceH - Replacement of ceramics & catalyst

12

Chemrec technology ready for industrial scale and can be built by world-class EPCs with adequate risk

allocation

• EPC 1: …one of few mature and feasible technologies for large-scale production … to produce fuels from forest-based biomass ...”

• EPC 2: “...in principle willing to provide customary EPC wrap around guarantees ...”

• EPC 3: “...LSTK service with customary wrap around guarantees ... ”

• Oil major evaluation (10 experts): “ No showstoppers for industrial scale-up”.

• Piteå demo plantproducing methanol and DME using commercial processes.

Piteå, 2nd gen, >21 000 hrs

New Bern, 1 st gen, 47 000 hrs

13

Chemrec Status as per January 2013

13

� Dec 31, 2012: Chemrec Piteå companies including pilot plants sold by

Chemrec AB to LTU Holding AB,

� Jan 1, 2013: 17 pilot plant staff employed by LTU.

� Dec 31, 2012: License agreement between licensor Chemrec AB &

HaldorTopsøe with LTU and LTU Holding. Technology rights stay with

licensors.

� Jan 30, 2013: Consortium Agreement between parties involved in

continued R&D.

� Chemrec has reduced staff awaiting long term stable regulations for

advanced biofuels. Two Chemrec Stockholm staff temporarily on leave

assigned to LTU

� Continued operation of the plants as part of LTU Biosyngas Program

10/18/2009 16

FLARE

Raw Syngas

GREENLIQUOR

Black Liquor

GAS COOLER

Oxygen

Atomizing medium

GASIFIER

QUENCH

C.W

BFW

MP-Steam

Weak Wash

CLEANSYNGAS

BFW

SULPHUR ABSORPTION

Condensate

White/Green Liquor

LP-St.

14

LTU Biosyngas Centre Program

15

The BL to BioDME facility is the backbone in the LTU Biosyngas Centre Program

DP-1Plant

WGShift

AmineWash

MeOHSynth.

DMESynth.

Distil-lation

ActiveC Abs

BlackLiquor

O2

BioDME

16

LTU Biosyngas Program planned for 2013-2016

DP-1Plant

WGShift

AmineWash

MeOHSynth.

DMESynth.

Distil-lation

ActiveC Abs

Electro-lysis

FuelCells

CatalyticProcess

Development

ETC EFgasifier

Cleaning

Membranes

Torrefied Mtrl

Powder

BlackLiquor

Pyrolysis oil

O2H2

CO,H2

CO2

BioDME

BioMeOH

Others

Existingfacilities

The RenewableSyngas Highway

25-30 bar > 100 bar

Future development

WP1 Pilot scale experimentsWP2 Catalytic gasificationWP3 Solid fuel gasificationWP4 Novel syngas cleaningWP5 Catalytic conversionWP6 Containment materialsWP7 Field testsWP8 Electrofuels and new concepts

WP1

WP2

WP3

WP4

WP5

WP6

WP7

WP8

H2O

1711/26/2013

17

Biomass flow from the forest can be increasedadding pyrolysis oil to the black liquor flow

PulpMill

Forest

Saw-mill

Pulp

WoodProducts

PulpMill

LogsPulp

Wood

RecoveryBoiler

Combined Recoveryand Fuel Generation

ForestResidues

Fuel

TOMORROW (3)

POProduction

18

WP2: Co-gasification BL/PO – some impressions from the lab

TGA and DTF lab activities during spring 2013

PO/BL mixing study• Lignin precipitation needs to be

considered above 20-25% PO

• No solids up to 20% PO

19

WP 2: Co-gasification of BL and PO offers many potential advantages

All calculations thus assume that BL/PO can be gasified at same temperature as BL is today.

Syngas Capacity increases about 100% by adding about 25% PO to the BL (by weight)

Energy efficiency for gasification of added PO is 80-85%

Figure shows simulated increased production of final liquid biofuel product at fixed BL feed (i.e. for specific mill)

Figure shows simulated gasifier energy efficiency of total mixed feed (solid) and for added PO (dashed)

0%

50%

100%

150%

200%

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300%

350%

400%

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du

ctio

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syn

gas

en

erg

y)

PO mix (part of total feed)

50%

55%

60%

65%

70%

75%

80%

85%

90%

95%

100%

0% 10% 20% 30% 40% 50%

CG

E

PO mix (part of total feed)

SF-LHV total

H2CO total

SF-LHV incr PO

H2+CO incr PO

20

WP 2: Key physical properties of PO/BL mixtures are promicing based on lab tests

0,01

0,10

1,00

10,00

100,00

1 000,00

0,1 1 10 100 1000 10000 100000

Sh

ea

r v

isco

sity

(Pa

s)

Shear rate(s-¹)

0%

10%

20%

30%

0

5

10

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25

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35

40

45

0 10 20 30 40 50 60

Su

rfa

ce

te

nsio

n (

mN

/m

)

Time (s)

Hanging droplet 100°C

Black liquor

10% pyrolysis oil

20% pyrolysis oil

30% pyrolysis oil

Viscosity Surface tension

21

WP2: Drop tube furnace experiments shows carbon conversion of PO/BL mixtures to be at

least as good as BL alone

Gasification ash microscopy(same magnification)

BL at 1000˚C BL at 1200˚C

PO(20) /BL(80) at 1000˚C

22

WP2: Techno-economic study co-gasification- preliminary results indicate good profitability

• Case study: Rottneros Vallvik– medium sized pulp mill

– good data from black liquor gasification study available

• Methanol plant alternatives evaluated – Black liquor gasification ~200 MW BL

– Two co-gasification alternatives • Extend methanol production by adding 25% and 50% pyrolysis oil

• Preliminary results indicate very favorable production cost for realistic pyrolysis oil price scenarios– Economies of scale and high efficiency contribute

23

WP2: Techno-economic study co-gasification- preliminary results indicate good profitability

• Case study : small/medium sized pulp mill• Methanol plant alternatives

– Black liquor gasification ~200 MW BL

– Two co-gasification alternatives – 25% and 50% pyrolysis oil

0

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6000

7000

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9000

300 400 500 600 700 800 900 1000

MeO

H p

rodu

ctio

n co

st [S

EK

/ton]

PO cost [SEK/MWh]

Case 25

Case 50

MeOH production cost • First plant CAPEX@10% annuity• Nth plant will give lower CAPEX

MeOH price reference levels for low-blend into gasoline• Pessimistic 6500 SEK/t based on 2011Rotterdam EtOH price volume equivalence

• Realistic 8500 SEK/t projection based onRED and proposed ETD (biofuel mandate)

MeOH production cost

Pessimistic price scenario

Realistic price scenario

24

Potential to test Liquid Organic Waste (LOW) in the LTU Green Fuels Plant

DP-1Plant

WGShift

AmineWash

MeOHSynth.

DMESynth.

Distil-lation

ActiveC Abs

Electro-lysis

FuelCells

CatalyticProcess

Development

ETC EFgasifier

Cleaning

Membranes

Torrefied Mtrl

Powder

BlackLiquor

Pyrolysis oil

O2H2

CO,H2

CO2

BioDME

BioMeOH

Others

Existingfacilities

The RenewableSyngas Highway

25-30 bar > 100 bar

Future development

H2O

LOW

25

Fuels and chemicals from organic waste- liquefaction opens new opportunities

MethanolDMEGasolineDiesel…

??

Fertilizer

GasificationSynthesis

Liquefaction

26

Fuels from organic waste- via liquefaction, gasification, synthesis

Fuels orchemicals

Liquefaction(alkali, heat)

Fertilizer

Catalytic gasification(oxygen, 1000°C)

Catalytic synthesis

Organic waste

Liquefiedorganicwaste

Recycledalkali

Synthesis gas

27

According to lab tests LOW liquids gasifies more easy than black liquor

The analysis above is based on a first order model fitted to the gravimetric data

0

0,01

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895 900 905 910 915 920 925 930 935 940 945

TG

A g

asi

fica

tio

n

rate

Temperature

BL

LOW2

LOW3

LOW4

LOW 1

LOW1: Pig manureLOW2: Meat and bone mealLOW3: WWT sludgeLOW4: Meat and bone meal

LOW1

LOW2 LOW3

LOW4

28

Feedstock study – fuel from organic waste(IVL Swedish Environmental Research Institute)

• Selected feedstocks– Liquid manure

– Chicken manure

– Slaughterhouse waste

– Biogas digestate

– WWT sludge

• Selected countries• Potential• Price• Alternative use

29

Many potential applications of catalytic gasification – long term research

Now :

• Black liquor

• Pyrolysis oil + black liquor (BL)

Potential future developments :

• Liquefied organic waste (LOW)

• Pyrolysis oil + liquefied organic waste

• Pyrolysis oil + Alkali salts (ALK)

• Solid biomass (SB) impregnated with alkali salts

PO

BL LOW

Alk

SB

Alkali containing feedstock

Alkali addition or co-gasifiaction

30

Future Energy System Scenarios– The need to look at the total cost of a new energy system

– An example from the marine sector

– An example from the HD vehicle sector

31

(European Commission Proposal dated January 24, 2013)

From Page 2:

From Page 3, under leagel elements:

32

“Well to Wheel” Qualitative Cost / Complexity Analysi sTypical comment: “The fuel must comply with existing infrastructure”Implying: Very complicated/costly with new infrastructure

FEEDSTOCK CONVERSIONDISTRIBUTION(incl. to vehicle)

USE

High

Low

-Costs-Env. friendly

-Efficiency-Costs-Env. friendly



Cost /Complexity

Perspective of the energycompanies

Perspetive of the enduser

Perspetive of the enduser

33

“Well to Wheel” Qualitative Cost / Complexity Analysi s

DME: fossil / renewable


USE

Low





High

Cost /Complexity

34


Methanol: fossil / renewable


USE

Low





High

Cost /Complexity

35


Hydrogen


USE

Low





High

Cost /Complexity

36


LNG: fossil / renewable


USE

Low





High

Cost /Complexity

37

Vision for a Methanol based Energy System1. today

Natural gas

Fossil MeOH

Methanolplants

Chemical industry

Via Ports

38

Vision for a Methanol based Energy System2. + methanol as bunker fuel

Natural gas

Fossil MeOH

Methanolplants

Chemical industry

Via Ports

Ports 1 2 n nn

M e t a n o l

Marine sector

39

An example where an international agreement results in a fundamental

rethink:

IMO, International Maritime Organization, on new sulphur levels in bunker fuels

coming into force 1 January 2015

40

Background to the new sulphur emission legislation:The Shipping sector’s partin the total sulphuremissions is very big

73%

11%

15%

Fuel

Road trafficAviationShipping

74%

12%15%

CO2

54%

5%

42%

NOx

27%1%

73%

SOx

Source: ScandiNAOS AB

41

Upcoming regulations for Marine FuelsSulphur level in bunker fuels must be < 0.1% by 201 5

0

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6

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10

12

14

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0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000

IMO NOx Technical code

NOx Tier II - 2011 (Global)

NOx Tier III - 2016 (NOx emission control areas)

g NOx/kWh

rpm

Source: ScandiNAOS AB

42

Price scenarios for Alternative Bunker Fuels

Well head:10 €/MWh

4 USD/MMBtu

Ex works:25 €/MWh

Ex works:20 €/MWh

Port price:34 €/MWh

Alongside ship:37 €/MWh

FOB Zeebrugge:30 €/MWh

Alongside ship:46 €/MWh

Brent Crud landed:47 €/MWh

110 USD/bbl

MGO Port price:57 €/MWh

HFO Port price:38 €/MWh

METHANOL

LNG

CRUDE OIL BASED FUELS

GOTHENBURG

GOTHENBURG

GOTHENBURG

Freight:60-70 USD/t

Source : Stena and Chemrec

43

Stena Methanol Pilot Project, Gotheburg

Item LNG MethanolHandebility Liquid at -163˚C,

Atmosperic PLiquid at ambient T and P

Storage Cryogenic handling; Space demanding

Can be stored as bunker oil

Cost of main storage in port

500 MSEK *) 50MSEK *)

FeedershipR’dam - Gbg

500 MSEK *) 0 MSEK; With today’s methanol tankers

Bunker vessel 300 MESK *) 15 MSEK *)

Rebuilt of ship, total 25 MW

250 MSEK 100 MSEK

Total cost diff 1550 MSEK / 180 MEUR 165 MSEK / 20 ME UR

*) First time investmentSource: Stena

44

Stena Germaica is planned to run on Methanol starting early 2015

Fuel: 25 000 tons of MeOH / year

Source: Stena

45

Stena’s Global Methanol Project(Initial timeplan for converting Stena’s SECA fleet )

Source: STENA and Effship

Methanol consumptionWill approach 1 million tons

By 2018

46

Vision for a Methanol based Energy System3. + methanol to DME for HD trucks and industry

Natural gas

Fossil MeOH

Methanolplants

Chemical industry

Via Ports

Ports 1 2 n nn

M e t a n o l

Marine sector

Heavytransports

DME DME

Energy usage

Distribution

47

Extended Volvo field test8 trucks, 2013-01-01 to 2014-06-30

0

100000

200000

300000

400000

500000

600000

700000

800000

900000

1000000

km

Date

Total Field test mileage

(1000 Km / 1000 mi) Status2013-04-08

TargetJune 2014

Total mileage 970 / 603 1 475 / 917

1 truck 200 / 124 300 / 186

Extended field test

48

Fuel Distribution

Piteå

Stockholm

Jönköping

Göteborg

European Project BioDME7th Framework Programme48

• Available technology modified for DME

• Safety regulations based on LPG

• ~200 k€ per filling station (+33% vs diesel)

• Easy to achieve

Four filling stations

200 m3 storage tank in Piteå

34 m3 trailer

49

Fuel consumption

European Project BioDME49

TruckApplication

Gross weight(Min/Max/Avg)

Typical FC Diesel Equivalent(l /10 km & mi/gal))

FH-787Regional and local haul

14/26/21 ton 2.3 / 10.2

FH-711long haul

25/50/ ton 4.1 / 5.7

FH-842local start/stop

21/57/53 ton 6.1 / 3.8

Volvo through their US branch on June 6, 2013 decided to start commercial production of

DME fuelled vehicles in the US in 2015.See various films at:

http://www.youtube.com/watch?v=L946kk7_NIEThe link includes:

DME – “The future is here”DME – “It is all around us”

and other material.

See also:

www.biodme.euBioDME Video

http://www.youtube.com/watch?v=cF1F7luFpnc#t=13

Volvo US DME truck

50

Vision for a Methanol based Energy System4. + providing system with renewable methanol from biomass

Natural gas

Fossil MeOH

Methanolplants

Chemical industry

Via Ports

Ports 1 2 n nn

M e t a n o l

Marine sector

Heavytransports

DME DME

Energy usage

Distribution

Biomass

Pyrolysis

Gasificationof biomass

Gasification Pulp mill

Renewable MeOH

Bio

mas

s

Bio

mas

s

MeOHMeOH

51 51

DME Fuel Station

BioMethanol Production

DME Production

DME Terminals

FossilMeOH

Source : Chemrec

Scenario for Introduction of DMEas a Fuel in Sweden combined

with fossil / renewablemethanol

52

Scenario for Introduction of renewable / fossil DME and methanol in Europe

52

5

2

MeOH bunker terminals/DME Production

Green MethanolProduction

Fossil MethanolImport

Source : Chemrec

53

Vision for a Methanol based Energy System5. + providing system with renewable methanol from waste

Natural gas

Fossil MeOH

Methanolplants

Chemical industry

Via Ports

Ports 1 2 n nn

M e t a n o l

Marine sector

Heavytransports

DME DME

Energy usage

Distribution

Biomass

Pyrolysis



Renewable MeOH

Bio

mas

s

Bio

mas

s

MeOHMeOH

GasificationLiquefact.

Nutrients MeOH

Wastes

54

Fuels from organic waste- via liquefaction, gasification, synthesis

Fuels orchemicals

Liquefaction(alkali, heat)

Fertilizer

Catalytic gasification(oxygen, 1000°C)

Catalytic synthesis

Organic waste

Liquefiedorganicwaste

Recycledalkali

Synthesis gas

55

Vision for a Methanol based Energy System6. + providing system with renewable methanol solar and wind

Natural gas

Fossil MeOH

Methanolplants

Chemical industry

Via Ports

Ports 1 2 n nn

M e t a n o l

Marine sector

Heavytransports

DME DME

Energy usage

Distribution

Biomass

Pyrolysis



Renewable MeOH

Bio

mas

s

Bio

mas

s

MeOHMeOH


Nutrients MeOH

Wastes

SOEC*

MeOH

CO2, H2O, electr.

56

Sun Energy + CO 2 + H2O

Source : Stena Rederi

57

Maybe an interesting area to study for the “Industrial Energy-Related Technologies and Systems”

Natural gas

Methanolplants

Via Ports

Ports 1 2 n nn

M e t a n o l

Heavytransports

DME DME

Distribution

Biomass

Pyrolysis



Renewable MeOH

Bio

mas

s

Bio

mas

s

MeOH MeOH


Nutrients MeOH

Wastes

SOEC*

MeOH

Harbor Companies

Shipping Companies

HD Transport Industry

Chemical Industry

Clean energy providers

MethanolIndustry

Waste ManagementIndustry

Renewable Fuels Industry

CO2, H2O, electr.

58

In Summary – Part 1• Black liquor (BL) gasification works. • Presence of alkali in the BL fuel results in comple te

carbon conversion at around 1000 deg C gasification temperature

• Laboratory work indicates that pyrolysis oil can be mixed with BL in significant amounts and that the catalytic effect still results in full carbon conve rsion at around 1000 deg C

• At a mix of 25% PO in 75% BL (dry basis) the syngas generation increases with about 100%

• Lab scale tests indicates that alkali supported gasification can be extended to other feedstocks su ch as manure, WWT sludge and meet and bone meal.

59

In summary – Part 2� New SECA regulation demands new, low sulphur bunker fuels� Methanol can become a cost effective bunker fuel al ternative,

cheaper and simpler to use than LNG� Bunker Methanol infrastructure in harbors can stimu late DME

production at optimum locations from a distribution point of view

� BioMethanol can be transported to the bunker Methano l infrastructure / DME production facilities and mak e the DME (and methanol) partly renewable

� It is cost effective and comparably simple to intro duce a new fuel in the HD transport sector which uses about 25 % of all transportation fuels (relates to Sweden but is sim ilar in rest of Europe)

60

Research partners and sponsors from 2001 until today

methanol, a multi source and multipurpose energy carrier

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