Production of Methanol Sustainably

and

Related Engine Technology

Final reportWorkshop groups summary

2

• Methanol is an excellent fuel for internal combustion engines, especially for Otto but also forDiesel type engines with appropriate technical adaption.

• Methanol is a ready available fuel. Methanol produced from renewable sources couldseamlessly be introduced to the methanol supply to shift towards a fully renewable fuel.

• Methanol burns very cleanly with low NOx and particulate (soot) emissions and contributesto reduced emissions when mixed with typical fuels.

• Methanol is toxic if ingested, but there are methods, which could be used to avoid accidentalintake.

• Methanol burns with an almost invisible flame but fuel grade methanol containing lubricantsand possibly other additives (e.g. gasoline) could make the flame visible. In case of fire, paintand other nearby materials would also cause smoke and a visible flames.

• Methanol is totally miscible in water and easily degrades in the environment.• Methanol has around half the energy density (15.8 MJ/liter) of diesel or gasoline. This is not

considered a large problem for use in ships, since it can be stored in space usually reservedfor ballast water tanks.

• Methanol-fuelled engines can be constructed to be more efficient than gasoline or dieselengines.

Methanol Basics

Introduction.............................................................................................................................................................3Now and Towards the future - a road map.........................................................................................................5Summary group 1 – Methanol Engines and Engine Technology................................................................... 7Summary group 2 – Methanol chemistry –Technologies for greener production..................................... 13Summary group 3 – Industrialisation of efficient and sustainable methods...............................................16

3

The ongoing globalization and development of international trade – which is keyto our standard of living, wealth and quality of life – is dependent on transportsof all kinds. Maritime transports counts for the by far largest transport work witha very high degree of energy efficiency but is yet consuming large quantities offossil fuel, mostly of low quality, and with environmental consequencesaccordingly.For the transport industry in general, including the maritime one, the society hasformulated requirements and targets aiming at reducing the emissions andultimately aiming at clean and GHG neutral energy supply/energy conversionsystems.The PROMSUS WORKSHOP provided opportunities for scientists andindustrialists within the fields "green fuel production" and "engine technologies"to present and discuss recent results and leads.The workshop results included- Suggestions for road maps for the development of engine technologies which inthe best way can utilizing identified methanol/alcohol fuels with regards tocomposition and qualities,- Proposals how to produce these qualities as green as possible and- Identification of what challenges that lie ahead to implement the findings in theshort, medium and long perspectives.

Introduction

Per Fagerlund Bengt Ramne

President of ScandiNAOS AB Managing Director ScandiNAOS AB

PROMSUS Coordinator Professor of the Practice

Chalmers University of Technology

4

Welcome and introductionPer Fagerlund, ScandiNAOS AB

Super-Efficient Methanol Engines using Spark Ignition and Exhaust Heat RecoveryDr. Daniel Cohn, MIT

Alcohol Compression IgnitionProf. Bengt Johansson, Lund University

Use of methanol in internal combustion engines – status reviewLennart Haraldsson, Wärtsilä

Methanol Synthesis from Renewable SourcesJohn Bøgild Hansen, Haldor Topsoe

Beyond Oil and Gas: The Methanol EconomyProf. Surya Prakash, USC

Closing the Fuel Cycle through CO2 Capture from AirDr. Klaus Lackner, Columbia University

Power to Liquid (PtL) and Power to Gas (PtL): an option for the EnergiewendeDr. Alberto Varone, IASS

Methanol Industry OutlookJason Chesko, Methanex

Converting Carbon Dioxide to Methanol FuelK-C Tran, Carbon Recycling International

Renewable Fuels – Opportunities to Grasp and Barriers to OvercomeIngvar Landälv, Luleå University of Technology

Methanol Global Market AnalysisWolfgang Seuser, MMSA

The PROMSUS workshop was held over two days. The first day consisted of presentationsand discussions in plenum where eleven of the participants presented different aspects ofthe use of methanol; from combustion and methanol engines to methanol chemistry and theoutlook for the methanol market. During the second day discussions took place in threegroups where abstracts of the discussions are published in this folder. The speakers are listedbelow.

5

It is not expected that there will be one single energycarrier which will be the "solve-all" solution for comingdecades. Oil based fuels will continue to dominate themaritime industry for many years – especially for oceangoing ships. Introduction of gas based marine fuels (LNGand methanol) is gradually taking place and will be used inparallel with the oil based fuels over a long period of time.The gas based fuels will increasingly be diluted with theircarbon neutral versions as CO2 emission rules gainground.The choice of fuel will be highly influenced by a numberof socio-economic and political factors. Local availability,price and environmental rules are the main drivers.By developing methanol engine technology anddemonstrate its economy, availability, efficiency andcapability to fulfil the environmental requirements of thesociety a demand for methanol engines and methanol fuelis created – a demand that per se is a powerful driver forfurther development of both engine and methanol fueltechnology.Increasing environmental focus from the society will pushadoption of rules calling for lower emissions includingGHG. However, there will also be arguments for pushingintroduction of new stricter rules further into the futurein order to allow the industry time to adopt.Based on the scientific project Effship, powerfullysupported by Stena rederi, the third largest RoPax ferry inthe world, Stena Germanica, is presently (2014)converting her four main engines (four stroke) to burnmethanol with diesel fuel pilot ignition. SimultaneouslyWaterfront Shipping (Methanex subsidiary) has orderedseven 50,000 dwt. product-carriers to be built andequipped with two stroke engines burning methanol withpilot ignition. The technology also permits the engines tobe operated entirely on diesel fuel should so be desired.The Classification Societies have been working onmethanol from their side. DNV GL has since July 2013tentative rules for low flashpoint liquid as fuel (Class

notation LFL) and Lloyd’s Register has similar rules indraft.For larger ships in worldwide service, or with desiredflexibility for worldwide service, methanol with pilotignition with alternative diesel only will be the preferredtechnology both for conversions and new buildings forthe years to come.HFO will be phased out as a HFO treatment installationis costly, heavy and space consuming, expensive to operateand will require end of the pipe equipment to satisfyenvironmental requirements.

For smaller ships with engines (250 kW to 1,250 kW)designed for high quality diesel fuel (like Euro V) andoperating in areas where high demands on low pollution isat hand (like inland waterways), methanol only enginesoffers an interesting alternative with lower fuel cost andhigher engine performance than the diesel alternative.Engine technology for methanol only is proven both forOtto and Diesel combustion, requires only one fuelsystem and has lower emissions than diesel fuel pilotignition due to the absence of diesel fuel.Methanol only engines are presently not included in anyknown engine makers program. To make such enginesavailable, conversion kits have to be developed and

Now and towards the future - a road map

6

applied to industrial standard engines. With conversionkits at hand, this can be done in a repacking industrysimilar to the present marine repacking of industrialstandard engines.Extensive scientific research work is ongoing at LundTechnical University and at MIT regarding how thespecial properties of methanol can be best utilized ininternal combustion engines. Very promising resultspointing at considerably improved efficiency andperformance are confirmed in laboratory scale. Afterindustrial confirmation, the new technologies can beincorporated in standardized conversion concepts thusadding high efficiency to the previous environmentalquality. In due course the new combustion technologiescan also be utilized in large ship engines improving theefficiency further from the initial methanol conceptswhich are introduced today.Promising technologies for greener and more efficientproduction of methanol out of natural gas are alsoconfirmed in laboratory scale. Methods to producemethanol out of bio-feedstock and out of capturedcarbon dioxide and hydrogen are being demonstrated ondemonstration plant level. The technology is verified inthese plants before commissioning of full scale

commercial plants that are on the planning stage.The requirements from the marketplace are the drivers for itsindustrialization. This in turn is driven by introduction of cost-and energy-efficient methanol engines that can meet the presentenvironmental requirements of the society and with capabilityto meet upcoming future environmental demands.

The conclusion of the PROMSUS workshop is that theMethanol Economy, as described and developed by theNobel Laureate George Olah together with Surya Prakashand Alain Goeppert, has, in the Maritime Industry, startedto demonstrate, in full industrial scale, its economical,technical and environmental qualities and its capacity toserve as a forerunner towards a transport industry basedon sustainable fuels and high efficient engines.

A full day open seminar was arranged after the Workshopwhere the secretaries and delegates of the Workshoppresented the conclusions of the Workshop. Some 90representatives from the maritime industry participated.Material from the workshop, reports (Effship etc.),methanol news, presentations and more can be found atwww.marinemethanol.com.

7

The summary is divided in two sections. First of alldemands that methanol engines need to meet. Thesedemands are further divided according to when they areexpected to apply; demands for an introduction today anddemands for the future in regards to higher efficiency andstricter environmental standards. The second part is areview of possible methods, both conventionalcombustion methods adapted for methanol and morenovel combustion cycles that exists on laboratory andprototype scale but is yet to be found in commercialapplications.

Demands for alcohol enginesThe demands that applies to any engine that is to be usedin marine applications also applies to a methanol engine,including safety and reliability requirements. For asuccessful introduction of methanol engines they need tobe just as good, or better, compared to the enginescurrently in operation. Upcoming and future emissionregulations also applies to methanol engines these has tobe met as well. As methanol burns considerably cleanerthan oil derived fuels the challenge to meet these demandsmight be easier but has to be evaluated for every engineconcept. While some engine concepts may meet all ormany of these requirements with relative ease, othermight still need exhaust gas treatment, e.g. for NOxremoval.

Demand today (conversions):Alcohol engine solutions which are targeting conversionof existing engines have to be adapted for alcoholic fuelsbut do not have to be optimized. Meaning that thefunctionality of the engine would be similar to anordinary diesel engine without taking advantage of the

alcoholic properties that could improve the efficiency on apurpose built alcohol engine. These optimizations wouldhowever lower the efficiency when the engine operate onconventional diesel fuel.

SafetyThe methanol engines need to be at least as safe as anyother engine alternative. This includes fire safety wheremethanol compared to ordinary diesel requires someadditional measures due to the low flashpoint. In general,low flashpoint fuels have been prohibited for marine usebut are becoming more common as LNG ships havegrown in numbers. The low flashpoint introducesrequirements on leak detection and modifications on theventilation systems as well as insulation of electricalsystems and operational guidelines to prevent sparks andstatic electricity that might ignite possible methanol fumes.The fact that methanol burns with a nearly invisible flamealso poses additional demands on the fire detectionsystems and additional detection points and detectionsystems might be necessary.On the other hand methanol fires are extinguishable withwater and have been used in motor racing for increasedsafety as the heat release rate from a methanol fire iscomparatively small and the fire zone is contained to thecentre of a methanol spill.

RobustnessIt is important that a proposed system is well understoodand tried before introduction to the market. A poorlyimplemented system will not only cause problem for theoperator but might also severely delay the introduction ofmethanol on a wider scale.

DurabilityIf any ship-owner is going to invest in methanol enginesthe durability need to be equal or better than currentengine models. Manpower is a considerable portion of therunning costs and increased costs due to service time andspare parts is not be acceptable.Material compatibility in the engines and auxiliary systems

Summary of the discussions in group 1 – Methanol Engines and EngineTechnologyWorkgroup leader: Tommy Bjorkqvist, TBAB TechnologySecretary: Bengt Ramne, ScandiNAOSParticipants: Daniel Cohn, MIT, Ingemar Denbratt, Chalmers,Lennart Haraldson, Wartsila. Bengt Johansson, LTH, PatrikKlintbom, Volvo, Soren Udd, SICEC.

8

need to be considered as well as the low viscosity thatrequires additional lubricating systems as the fuel itselfdoes not provide enough lubrication.

Equal or better efficiencyA methanol engine need to provide the same or higherpower to weight ratio as a diesel engine and an engineconversion to methanol should not reduce the power ofthe engine. Dual fuel concepts based on port injectedmain fuel (methanol) will have to reduce the compressionratio due to knocking concern and in order to maintainthe same power the bore of the cylinder needs to beincreased, meaning a quite complicated conversion job.This will also reduce the efficiency of the engine whenrunning in diesel-only mode. A conversion applying themethanol-diesel concept means that both the pilot fuel(diesel) and the main fuel (methanol) are injected near topdead centre. With this concept the original compressionratio can be maintained which will provide equal or betterefficiency in methanol-diesel mode and maintain theefficiency for diesel-only mode.

Fuel flexibility (full output with backup fuel) will be an advantageWhen introducing methanol for conversion of existingengines, fuel flexibility is an advantage. This is especiallytrue for larger vessels that already today have the optionof using either MGO or HFO. The uncertainty about thefuture methanol price and availability emphasizes theadvantage of fuel flexibility.

Emission meeting legal requirementsDepending of where the engines are operating, differentrules and regulations apply. Alcohol engines will meet anyparticulate or sulphur limits (eg. sulphur content limit to0.1 % inside emission control areas from 2015).Compliancy with current Tier II NOx emission regulationfor ocean going ships should pose no problems. Whetheror not methanol engines will require after-treatmentsystems to comply with the Tier III standard, enteringinto force for new-buildings 1st of January 2016, willdepend on the type of methanol engine technology that isused.For inland waterways EU Directive 2009/30/EC appliesthat stipulate a maximum sulphur content in the fuel to 10

mg/kg (0.001 %), the same as road transportation. Theregulation came into force January 1st 2010.

Cost efficientFor the introduction of a new engine the cost efficiencyshould be equal or better compared to current generationdiesel engines. This is highly affected by the fuel price butalso the service costs. Regulations and governmentincentives are important factors.

Short off hire conversionThe complexity of a conversion is also a critical factor. Inaddition to the actual cost for the equipment and theman-hours for conversion the ship-owner need toconsider the loss of income during the time the ship isoff-hire.

Additional demand 2025The future requirements of engines will be higher withregards to reduced emission but also for higher efficiency,reduced maintenance and lifetime cost.

Tier III complianceTier III NOx regulations will enter into force 2016 for theshipping industry. For smaller conversions of currentengines compliance with the Tier III might not benecessary but for next generation engines and newbuildings compliance will be required.

Fulfil EEDI index (Reduced GHG emissions)The Energy Efficiency Design Index (EEDI) required byIMO for all new ships above 400 GT is a measure of themass of CO2 emitted per unit of transport work(gCO2/ton-nm). A methanol engine should be efficient

9

enough to provide an alternative to lower the EEDI valuefor the proposed ship and thus provide a method forlowering the EEDI for a new ship design.

Fuel flexibilityFor large marine engines, dual-fuel operation meaning alsofuel flexibility might still be considered a benefit. Forsmaller marine engines and engines for land applicationsingle fuel methanol engines need to be available

Sufficient powerThe potential of increased efficiency that methanolprovides need to be utilized for increased power to weightratio.

Reduced PM emissionsExpected upcoming requirements for PM reduction willpromote methanol engines as virtually no soot is createdduring combustion. If pilot fuel is used to initiatecombustion some soot will be formed but the levelswould still be small.

On board emission measurements and monitoringIt is expected that performance and emissions will bemeasured onboard in real-time in order to monitorefficiency and regulation compliance

Additional demand 2050By 2050 emissions from engines are expected to be inpractical zero. This will require operation on fossil freemethanol.

Tier IV or V complianceDepending on the regulations alcohol engines should beable to meet upcoming emission limitations to the bestpossible extent without any need for exhaust gas aftertreatment. Technologies such as exhaust gas recycling(EGR) is likely needed to reduce NOx to allowed limits.

Ability to run on renewable fuelMethanol produced from renewable sources should reachvolumes that allow a gradual switch from fossil methanol.Highly dependent of availability, regulations and cost.Government incentives are likely needed. Notechnological barriers exist for phasing in renewablemethanol to existing supplies.

Single fuel option (diesel free operation)If methanol is successfully introduced to the marinemarket the requirement of fuel flexibility is likely todisappear or be smaller. If that is the case the enginecould be optimized for methanol with the possibility ofconsiderable higher efficiency.

Equal to emissions from land transport alternativesThe marine emission regulations are currently much lessstringent compared to the corresponding regulations forland transport. All projections point in the direction ofcontinously increasing international trade and increaseddemand for marine transportation work. Despite therelatively low emissions of greenhouse gases in relation totransported goods the emissions from the marine sector issubstantial. Converging regulations is not unlikely and thealcohol engine of the future should be able to meet strictemissions standards.

Recycling demandIt is expected that the total life cycle footprint of theengine will be considered. This will require improvementsin resource efficient production and recycling.

Engine ConceptsDifferent alternatives are possible for alcohol engines. Thetechnologies are divided in groups based on the expecteddevelopment time needed before being ready forintroduction to the market.It should be noted that there is no naming standard forthe combustion concepts, particularly for the differenceOtto combustion cycles. Fumigation is sometimes used todescribe the concept that is here called Premixed dualfuel. Likewise, Dual Fuel is often, as in this paper, used todescribe an Otto cycle with pilot fuel but can also be usedmore broadly to describe any engine that is able to operatewith different fuels.

Concepts todayMethanol­dieselThe methanol diesel engine relies on conventional dieselcycle combustion where a pilot injection of diesel fuel isused to initiate the combustion before a methanolinjection follows.

10

This concept will be used by Wärtsilä on Stena Germanicaand by MAN on seven new buildings for Waterfrontshipping. Wärtsilä use a single fuel injector capable ofdistributing both diesel and methanol whereas MAN hasfitted separate methanol fuel injectors.The advantage is high efficiency and no knockingconcerns. This provides the possibility to shift to dieselfuel mode with no reduction of power. As methanol isinjected to the ongoing combustion unburned methanol nthe exhaust gases is minimal avoiding formation offormaldehyde. The higher temperature and pressureduring combustion do however produce conditions forNOx formation. How much NOx need to be studiedfurther but it is not likely that upcoming requirements arepossible to meet without exhaust gas treatment.

Premixed dual fuelThe premix concept is currently used for LNG Dual Fuelengines. Similar to LNG, methanol is distributed to thesupply air in the inlet channel and thus is mixed with air inthe cylinder before combustion. A pilot injection of dieselis used to ignite the fuel mixture close to TDC, similar toa spark plug in an ordinary Otto engine.When operating on methanol the engine will workaccording to the Otto cycle. This introduces thepossibility of engine knock which is avoided by lowerpressure in the cylinder and increased bore to maintain

high power. The drawback is somewhat lower efficiency indiesel only mode, during which the engine worksaccording to the Diesel combustion cycle.Premixed combustion greatly reduces NOx emissions dueto lower peak pressure and temperature whileformaldehyde formation might be a concern. The premixcombustion concept also exposes the inlet manifold,valves, piston and cylinder liner to unburned methanoland thus material compatibility must be considered as wellas methanol contamination of the lubricating oil due toblow by gases.

Pre chamber spark ignitionA concept similar to the premixed dual fuel is if insteadof pilot fuel a spark plug is used to ignite the fuel-airmixture. Similar to spark ignited gas engines a rich fuel-airmixture is led to a pre chamber where combustion isinitiated by the spark plug. The flame propagation fromthe pre chamber in turn ignites the leaner fuel-air mixturein the cylinder.No diesel fuel is needed with lower emission levels in theexhaust gases as result.

Concepts in 2 yearsPre chamber spark ignitionSame as above.

Glow plugWhile the cetane number of methanol is too low forcombustion to only rely of the pressure and temperaturein the cylinder methanol has been shown to have goodhot surface ignition properties. Installation of a glow plugis therefore a possible method for a methanol engine.Investigation of spray pattern, piston geometry andsuitable glow plug location is important to optimize.

FumigationFumigation is similar to premixed concept but differ as towhen the fuel is mixed with the supply air. In thepremixed concept described above the methanol injectoris situated in the inlet manifold close to the inlet valves inthe cylinder head. In the fumigation concept methanol isinstead carburetted or injected to the air further upstream,before the compressor.Principle of fuel injector capable of distributing both

methanol and conventional diesel fuel.

11

The high heat of evaporation of methanol helps to coolthe inlet air mix during compression and as theevaporation occurs before the cylinder the combustiontemperature in the cylinder is higher compared to thePremixed dual fuel concept.Disadvantages are that it is more difficult to controlmethanol content in the exhaust gases and that that thematerial in the compressor needs to be compatible withmethanol.

Concepts in 2025Methanol­diesel Tier III (EGR or SCR)It is unlikely that the methanol diesel concept will be ableto meet tougher NOx emission standards on its own. Itmight be possible with the use of exhaust gas recycling(EGR), alternatively by using exhaust gas after treatmentsuch as Selective Catalytic Reduction (SCR).

Partial Premix Combustion (PPC)Simultaneous use of spontaneous ignition (as in a dieselengine) and premixed fuel in the cylinder (as in a ottoengine) have shown to have great potential for increasedefficiency and low emissions of NOx and sooth.In Partial Premixed Combustion a first injection of fuel isdistributed to the cylinder during the early stage ofcompression to form a lean fuel-air mixture in thecylinder, followed by a second injection close to TDC toinitiate combustion.

Reactivity Controlled Compression Ignition (RCCI)RCCI is a dual fuel engine combustion technology and isa variant of Homogeneous Charge Compression Ignition(HCCI). While PPC controls the ignition timing with a

second fuel injection RCCI controls the ignition timingand burn rate by combining fuels with differentproperties, such as gasoline or diesel or possibly methanoland diesel.RCCI provides more control over the combustion processthan HCCI and has the potential to dramatically lowerfuel use and emissions

Reformer enhanced methanol engineResearch on using reformer enhanced methanolcombustion is ongoing and has shown very goodpotential. The idea is to reform methanol to a hydrogenrich gas before injection to the engine. The heat for thereformer is recovered from the exhaust gas. The hydrogengas is more reactive than the methanol and thus higherefficiency is reached. For combustion control methanoldirect injection is used in combination with a knocksensor and computational monitoring.

Concepts in 2050Homogeneous Charge Compression Ignition (HCCI)Unlike diesel combustion HCCI injects fuel during theintake stroke. Unlike otto combustion, the combustion inthe HCCI engine is initiated by the compression which isincreased until the entire mixture reacts spontaneously.The main challenge is to control the combustion. Severalparameters need to be measured and fed back to anengine controller which has to regulate fuel amount,injection timing, and EGR amongst other parametersTo develop the engine control to get a stable operationduring various conditions will require quite extensiveresearch and development.

Principle of the methanol diesel concept. Air is compressed in the cylinder before a small pi lot injection of diesel fuelclose to TDC initiates the combustion. A larger methanol injection fol lows to maintain combustion.

12

General engine developmentClosed loop combustion controlIn order to reach higher efficiencies and bettercombustion control it is necessary to develop closed loopcombustion control systems. The current generation ofopen loop combustion control relies on a fixed set ofcalibration maps for different running conditions. Themaps are becoming ever more advanced but are notflexible enough to control more advanced combustioncycles such as HCCI with an increasing demand forprecise and flexible control systems.

After treatmentWith stricter emission regulations it is not likely that eventhe more advanced combustion cycles will be able to meetthe demands without after treatment of the exhaust gases.Development is needed to reduce the cost and weight of

similar systems for the marine sector.

EGRThe concept of exhaust gas recycling will be refined andfully utilize the potential with alternative cleaner fuel.

Cost of methanol engine developmentThe cost to develop the basic methanol concepts tomarket introduction will be in the range of a couple ofmillion euros per engine type. No fundamental enginedevelopment is required since the technology is wellestablished. The development will in general beadaptation of components and control systems.The more refined methanol concepts were thecombustion and energy recovery processes are optimizewill require significant more time and resources

Demands

Concepts

- Safe

- Robust

- Overal l availabi l ity (equal with diesel)

- Durabil ity (equal with diesel)

- Equal efficiency with diesel

- Fuel flexibi l ity (ful l output with backupfuel) wil l be an advantage

- Emission meeting legal requirements

- Cost efficient

- No power reduction compared tooperation on diesel

- Possible to make the conversion in ashort time in order to minimize theoff-hire cost

- Methanol-diesel

- Premixed dual fuel

- Pre chamber spark ignition

- Pre chamber spark ignition

- Glow plug

- Fumigation

- Methanol-diesel Tier I I I (EGR orSCR)

- PPC

- RCCI

- Reformer enhanced methanolengine

- Tier I I I compliance

- Fulfi l EEDI index (ReducedGHG emissions)

- Fuel flexibi l ity

- Sufficient power

- Reduced PM emissions (if IMOdecides)

- On board emissionmeasurements and monitoring

Today In 2 years 2025

€ 1 000 000 – 3 000 000 € 1 000 000 € 4 000 000 (proof of concept)Development effortEstimated developmenteffort to convert atstandard 1 MW dieselengine to methanoloperation

13

There are a variety of pathways for the production ofmethanol efficiently, economically and in a sustainableway. Their relevance will be different in the short, mediumand longer terms, but the diversity of technologiesreinforces the fact that methanol can be a very flexible,possibly sustainable and versatile liquid fuel. Similarconclusions are valid for dimethyl ether (DME), easilyproduced by bimolecular dehydration from methanol.The central idea of the workshop discussion was toscrutinize the general aspects of methanol as a fuel fromthe viewpoint of its use as marine fuel. Here are thesalient points made:• Methanol is an exceedingly good fuel for internalcombustion, especially for Otto but also for Diesel typeengines with appropriate technical adaption. It has anextensive track record being used in racecars and otherapplications since it is considered a high-octane and safefuel.• Methanol burns very cleanly with low NOx andparticulate (soot) emissions and contributes to reducedemissions when mixed with typical fuels.• Methanol is toxic if ingested, but there are additives,which could be used to avoid accidental intake. Methanoldispersion is quite safe and it is practiced, for examplemethanol is the major component of windshield wipingfluid.• Clean methanol burns with an almost invisible flame butfuel grade methanol containing lubricants and possibly

other additives (e.g. gasoline) would make the flamevisible. If additives are used in fuel grade methanol, it isimportant to ensure that it is not harmful when spilled.• Methanol is totally miscible in water and easily degradesin the environment.• Methanol has around half the energy density (15.8MJ/liter) of diesel or gasoline. This is not considered alarge problem for use in ships, since there is availablespace, which is only used for ballast in most ship types.This limitation can be overcome also for trucks and lightvehicles by the design of more efficient and lighterengines. For ships, the additional equipment generallynecessary for heavy fuel oil (HFO) treatment can beeliminated.• Methanol-fueled engines can be constructed to be moreefficient than gasoline or diesel engines.In order to make methanol available to the marketplaceand to efficiently promote it as a fuel in the short term,fossil-based methanol production is necessary. There aredifferent promising technologies that are being developed(e.g. partial oxidation, bi-reforming, oxidative bi-reforming, etc.) to produce methanol from natural (shale)gas more efficiently than the technologies used today (e.g.steam reforming, autothermal-reforming). Thesealternative technologies have been tested at the lab-scalebut not at full scale so far. An important question that

Summary of the discussions in group 2 Methanol chemistry –Technologies forgreener production

Workshop leader: Surya Prakash, University of SouthernCaliforniaSecretary: Selma Brynolf, ChalmersParticipants: Karin Andersson, Chalmers, Karin Pettersson,Chalmers, Richard Gebart, Luleå University of Technology, PerFagerlund, ScandiNAOS, Alberto Varone, IASS, Lars JPettersson, KTH, Dinko Chakarov, Chalmers, Klaus Lackner,Columbia University, Maria Grahn, Chalmers, Joanne Ellis,SSPA

14

remains is how cost effective these technologies are andhow one can reduce the carbon footprint of methanolproduction? Another way to produce methanol fromfossil sources is to produce it from gasification of coal (aspracticed in a large scale in China). The possibility ofproducing methanol in a distributive fashion fromstranded natural gas and gas that are flared today was alsohighlighted. The fossil routes to methanol couldpotentially be carbon neutral, but this would require thatthe carbon dioxide emitted during the production and thecombustion of methanol is captured and stored andpossibly recycled. Another option to define fossil basedmethanol as carbon neutral is if carbon is captured fromair, seawater or bioenergy and thereafter storedunderground. Efforts to achieve efficient carbon capturefrom air are being pursued world-wide.Biomass based routes to methanol could reduce thecarbon footprint of methanol compared to the fossilbased ones. Biomass gasification of black liquor followedby DME synthesis is practiced in a pilot plant (Chemrec)for a considerable time now in Sweden. The technologyhas been proven to work and can be considered mature.This route could therefore also be considered in the shortterm, but the biomass supply potential is limited andgeographically localized. It is possible to increase theoutput by blending the black liquor with fast pyrolysis oil.

Gasification of dry wood directly is also a possibility, butthis technology will need more development and testing atpilot scale before it can be commercialized. Currently, thecost for gasification and methanol synthesis is high withrespect to the fossil feedstock based production. There isalso a trade-off between scale of the production plant andtransport of the raw material. Fast pyrolysis can be usedin smaller scale to reduce the transport cost. Underdifferent circumstances there is a pathway to producemethanol from dry wood, from pyrolysis oil and fromblack liquor. The route via black liquor is expected to bethe most economically viable of these alternatives.Municipal waste is also a feedstock for methanolproduction even if it is mainly used for heat and electricityproduction today. Glycerol, a major byproduct ofbiodiesel production can also be gasified to producemethanol.Methanol can also be produced from CO2 and H2. This isindustrially practiced in Iceland today by CarbonRecycling International (CRI) using geothermal energy.The H2 originates from electrolysis of water and the CO2is captured from geothermal power production emissions.Clean water is needed for electrolysis and the water canpotentially be a limiting factor, but the water requirementis small when compared to biofuel production. It is alsopossible to produce methanol by different

15

electrochemical, photochemical and thermochemicalroutes in the future. The electrical energy to producehydrogen can be sourced from wind, solar (also avoidingtheir natural intermittency), hydro and even nuclear. Theenergetically most efficient and simultaneouslyenvironmentally friendly way of producing methanol isdirect photo-electrochemical CO2 hydrogenation, but themethods and materials for this scheme are still on researchat laboratory level.All these processes use CO2. The CO2 can be capturedfrom the air, the sea or exhaust gases of aluminum, steel,cement and coal (fossil fuel) burning power plants. Thebiofuel production facilities as well as the brewingindustry could be a good source of CO2. The moreconcentrated the streams of CO2 are the easier and moreeconomical is the capture of CO2 and its utilization.Simultaneously, it is important to account for the wholecarbon cycle when choosing CO2 source from the air,water and especially biomass in order to avoid additionalcarbon to be added to the atmosphere when the methanolis used. It was also brought up that air capture can havethe potential to be more cost efficient, compared todifferent more concentrated point sources of CO2 as thetransport of CO2 is quite costly.The price of electricity is the main cost factor/driver forthe electricity-based routes. The possibility to utilize andstore intermittent energy is one option that can beimportant in the short and medium term. Batteries aregood for storage over short periods of excess electricity,while fuels are more appropriate for storage over longerperiods of excess electricity. Methanol is a suitable liquidfor energy storage and as an energy carrier because it canbe easily transported. It can be used as a feedstock for thechemical industry, as a fuel or to produce electricity. Thedevelopment of electrolyzers with low capital cost couldbe an important step to boost the production ofhydrogen-based electrofuels including methanol. The costof the electrolyzer is argued by some to be the maincapital cost especially when they are used when there isexcess electricity, intermittently. In a long-termperspective, electrofuels such as methanol could also be

produced from renewable electricity on a more stable andconsistent level.It is important to demonstrate that methanol is anefficient fuel to produce and to consider its life-cycleimpact. So far there are not many studies evaluating theenergy efficiency and life cycle greenhouse gas emissionsfor the potential routes to methanol. A first screeninganalysis of some of the potential routes has been carriedout in a Master Thesis at Aalborg University. The studyindicates lowest CO2 emissions - compared to other fossiland biofuel pathways - both for methanol produced fromcaptured CO2 and for methanol produced via black liquor.It was also stressed that it is important to demonstrateexperimentally that the emissions from the combustion ofmethanol in internal combustion engines are relativelycleaner since there are limited independent studiesavailable today.Finally, the group stressed that there is a need for long-term stable governmental incentives to bring carbonneutral production technologies to the market. It isimportant that these incentives are developed immediatelyfor the biomass based routes as many projects are in thecrucial phase of deciding if the projects should be scaledup or shut down. For the shipping industry incentives forreducing NOx, SOx and particulate emissions can also beimportant. This could be a way to introduce methanol inshipping. Incentives based on energy efficiency andcarbon dioxide emissions emitted during the life cyclecould potentially be developed and used as well.Further issues that were brought up were the problemwith utilization of the heavy fractions from the refinery(that the shipping industry uses today) and utilization ofthe flare stack (at refinery and oil rigs). The group stressedthat there are other possible uses for this fraction otherthan ships. Ships deserve a cleaner fuel. The heavyfractions from the refineries that are today used in theshipping industry can be used in land-based industries,which have much better cleaner combustion possibilitiesthan the shipping industry. It is also possible to gasify thefractions to produce methanol.

16

Methanol production today and near futureMethanol production processes from natural gas are todayalready highly optimized. Production plants of 5000MTPD are commercialized and the general method tolower the production cost is to build larger productionfacilities (economy by scale). The bottleneck for the largerplants is generally on the distribution side. Mega sizedplants have been discussed and planned but are held backdue to uncertainty of long term stability of the feedstocknatural gas availability and price. The efficiency of amodern plant can reach about 70 % (e.g. 69 % at StatoilTjeldbergodden, Norway) in terms of energy conversion.Methanol production from renewable sources istechnically available but represents a vanishingly small partof the production volume at present. The biggest hurdlesare the high investment cost and the cost of feedstock,biomass. Uncertainties regarding regulations and fuelstandards also hamper investments in renewablemethanol, as well as other renewable energy carriers.Methanol promoters such as Stena, Chemrec, WärmlandsMethanol, are important if methanol is to becomerecognized as a viable fuel and for renewable methanol tobe seen as an alternative to methanol from natural gas (orcoal). Their task is to show that methanol is viable bothfor producer and consumer.For methanol production, in particular if sustainable, it isimportant to use the right technique for the rightcircumstances and to choose the most suitable locationwith regards to other nearby industries where synergiescan be found. This relates for example to availability ofcheap electricity, carbon dioxide and/or oxygen surplus,

all of which could be used for methanol production.To use district heating as a heat sink for the productionplants have previously been suggested but as the trend fordistrict heating is declining this is not seen as analternative. To improve the economic scope other sourcesfor excess heat should be considered, e.g. a pulping plant.In order to optimise a methanol plant, in particularsustainable, it is important to not only look atoptimisation of the plant but on the whole value chain.

Small scale plantsWhile larger plants generally provide better economicframework by economy of scale, smaller semi-movableplants could, if not too expensive, provide opportunitiesfor methanol production in locations where there is anexcess of low priced natural gas but no viable methods ofutilization. In connection with oil production a substantialamount of gas is flared, referred to as stranded gas. Thiscould provide a low cost feedstock for small to mediumscale methanol production.Areas of shale oil production where natural gas is flaredor even vented to the atmosphere have relatively shortlifetime and pipelines is often not an alternative. The localgeography might also prevent any construction ofpipelines. The Niger delta and offshore oil wells are otherlocations where small scale movable productions plantscould provide means to utilize this excess gas. Bargemounted or ship mounted production facilities aresuggested as an alternative.

Summary of the discussions in group 3 – Industrialisation of efficient andsustainable methodsWorkgroup leader: Thomas Stenhede ,WärtsiläSecretary: Joakim Bomanson ,ScandiNAOSParticipants: Per Alvfors ,KTH, Jason Chesko ,Methanex, RolandClift ,Surrey, Björn Hall ,StenaMetall, John B Hansen ,HaldorTopsoe A/S, Sjuar Haugen ,Statoil Fuel & Retail, IngvarLandälv ,LTU, Per Stefenson ,Stena Teknik, Henrik Thunman,Chalmers, K-C Tran ,Carbon Recycling International.

17

The challenge is to make the plants inexpensive enough tomake the investment viable. For small scale productionfacilities economy of scale is not an alternative but ifthere is a demand for sufficient number of units it mightbe possible to push prices to an acceptable level (economyof numbers).In order to introduce these plants regulatory steps toprevent flaring might also be necessary to promoteinvestments. The distribution of small scale methanolmight be a problem with regards to a LCA, but theenvironmental effects would be much preferred comparedto flaring or venting.

BiomassGasification of biomass is compared to production fromnatural gas not as developed. The main problems areimpurities and tars that are released during gasification,feeding of biomass to the gasifier, and to maintain highoperating time. A challenge is also to collect and transportbiomass in large enough volume to the methanol plantwhile keeping cost low.The gasifier at Chalmers achieves an efficiency of 80 %(to synthesis gas, a mixture of H2, CO and CO2) onenergy base from woodchips, where 20 % is consumedfor heat. The efficiency is traded versus higher tarformation and higher operating cost.It is important to take advantage of the local resourcesand local price levels. At some locations in the US residualwood is low priced and might be close to compete withnatural gas. In general the price difference is too high tocompete on economic terms without further incentives.

Black liquorBlack liquor (BL) has been identified as an advantageousfeedstock for producing methanol or DME. BL is a liquidpumpable chemical residual from the pulping processcontaining a lot of biomass energy; estimations suggestthat the available BL could be sufficient to supply ¼ ofthe automotive fuel in Sweden. The gasifier generatessyngas and recovers valuable chemicals necessary for thepulping of cellulose. A conventional pulp plant hasobtained an excellent energy balance, if now energy isextracted for synthesis gas production additional biomass

must be added to the plant for generating necessarysteam.Compared to conventional biomass gasification anadvantage with black liquor is that the collection ofbiomass is to a large extent already done by the pulp plant.By mixing pyrolysis oil and LOW (liquid organic wastethat has been concentrated and boiled to a slow-flowingmass) to black liquor the potential feedstock is enlarged.Common problems with pyrolysis oils containing alkalisare also negated in this process as they have shown toimprove the conversion.

BiogasBio-gas is gaining popularity, not least in Sweden wherebio-gas facilities have been started to produce bio-gasfrom biomass and feed gas into the already existinginfrastructure for natural gas. While not economical todaythe economy might change to promote upgrade of thebiogas to methanol. Production of bio-gas is similar tomethanol production; biomass is first gasified to synthesisgas which is synthesised to methane. By altering thesynthesis process methanol could be synthesised instead,alternatively the methane could be converted to methanolin the same manner as natural gas is used as feedstock.Methanol upgrade could also reduce the need of therather expensive step of CO2 removal from the biogas.By using the natural gas network to feed the methanol

Black Liqour that is used as feedstock for gasification inPiteå. Image courtesy of Chemrec.

18

plant there might open a possibility to buy greencertificates for the green gas provided to the network.Much like green electricity today the gas could be fedthrough a common network.

WasteGasification of waste (e.g. FLUFF from scrapped cars)where the other alternatives are burning or disposal,which causes costs, might provide an additional feedstock.Gasification of plastics has been demonstrated, the mainproblem is to get the waste in to the gasifier. Metalscontained in the waste might also be relatively easy toseparate which would provide a secondary benefit.By converting waste to pyrolysis oil it could possibly beused together with black liquor, LOW and pyrolysis oilfrom other sources.Residual oil composition will continue to degrade as morehigh value fuels will be produced and the market for HFOfor land based and sea based operations is likely to getsmaller, especially in ECA-areas. Lower quality residual oiland waste oil might be gasified if regulations and taxesmake it less economical to burn it for energy and/or ifupgrade of the oil is not economical.Synthesis gas from waste could be viable applying plasmatechnology. However such a plant requires substantialamount of electricity.

OtherElectrolysis of hydrogen for methanol production isanother route that can produce methanol with very lowclimate impact pending green electricity production. Theprinciple is similar to the Elygrid project where hydrogenis produced from excess electricity. 50 MW alkalineelectrolysers are probably possible today but the cost isstill too high.

Methanol qualityProduction of raw methanol to be used as fuel has beendiscussed for at least 30 years. The argument is that byallowing a less clean methanol grade the distillation stepof methanol production can be bypassed and thus energyis saved. Especially the last part of distillation whereethanol is removed is energy consuming. The capital cost

of the plant would also be somewhat reduced byabandoning distillation which represent about 10 – 15 %of the investment cost.It is debatable if grade AA methanol is really required bymost of the present buyers have been raised and it can beargued that methanol could very well be sold in threedifferent quality grades depending on requirements.Methanol engines is almost certainly not affected by anyethanol content in the fuel and also able to handle a quitehigh water content, which might actually help to reduceNOx.The argument against fuel grade methanol is that it wouldlimit the potential buyers of the methanol produced in aspecific plant but distillation could very well be performedat other locations or by the buyers if that is economical. Itshould be noted that it is not likely that direct methanolfuel cells would function well with fuel grade methanol.The ability for a market of raw methanol is viable thoughand especially for smaller producers abandoning thedistillation step would likely improve the prospects ofsetting up plants and maintaining a reasonable price level.Depending on available feedstock and technique, thewater content in the methanol may differ which must betaken into account.

Perception and introductionWhile believing that methanol is a good alternative for thefuture we must also recognize the risks and potentialdownsides early to be prepared and to avoid futureproblems that could cause a backlash against methanol. Inthat context, Statoil is developing fuelling systems foralcohol fuels where spills are prevented and tapping toopen containers is impossible. In addition to safetyconcerns this is also to reduce potential legislationproblems for ethanol fuels when crossing borders.We should also recognize that different fuels are suited fordifferent applications. DME is a proven fuel for heavyduty automotive applications and LNG works very wellclose to LNG terminals and for LNG carriers. We shouldnot oppose the “LNG lobby”, but recognize it.To promote methanol and the viable technologies for its

19

PROMSUS Organisational CommitteeCoordinator: Per Fagerlund, ScandiNAOS ABKarin Andersson, ChalmersJoakim Bomanson, ScandiNAOS ABBengt Ramne, ScandiNAOS ABPer Stefenson, Stena TeknikThomas Stenhede, Wärtsilä

August 2014, Gothenburg

PROMSUS SecretariatC/O: ScandiNAOS AB

Adolf Edelsvärds gata 1141 4 51 Göteborg

SWEDENinfo@scandinaos.com

Presentations and reports from PROMSUS are availableonline at www.marinemethanol.com

introduction and use as well as to give answers toquestions about use and risks promotion is needed. Somewebsites and organisations exist, e.g. The MethanolInstitute (MI) (www.methanol.org), Methanol Fuels(www.methanolfuels.org) and Marine Methanol(www.marinemethanol.com). (Marinemethanol.com wasset up before the PROMSUS workshop to answerquestions about methanol as a marine fuel but has yet notbeen promoted any further and still requires some workon the framework.)There should be short, concrete and honest datasheetseasily available on different fuels for comparison.The marine sector is viewed as a viable start for methanolfuel use but it is important to do it smart. Learn of pastmistakes of ethanol introduction and be prepared. Weneed to recognise problems and questions aboutmethanol.

Commercial and legislative barriersIn order to introduce methanol and give methanol equalstatus compared to other alternative fuels lobbyingpoliticians and policy makers is necessary. Some success

has been gained to include methanol at current time but itis still too often forgotten in discussions of future fuelswhere LNG ethanol, FT-diesel etc has gained much space.On a broader scale, MI is the only larger lobbyingorganisation promoting methanol but their resources arestill very limited compared to ethanol and LNGpromoters. An important step in North America is to getthe Open Fuel Standard Act passed by congress.For investments to go forward from the planning a stableregulatory and commercial framework is necessary. As oftoday several plants for renewable fuels have halted on theplanning stage despite substantial grants. The long termconditions are too uncertain for investors to be able to goforward and unless something is done quite soon the riskof these projects to move from halted to shut down islarge.The upcoming EU-elections provide a six month windowto prepare before the organisation has settled.Regulations have moved things in the past and are animportant tool to introduce alternative fuels.

The PROMSUS workshop was held in Gothenburg, Sweden, 6 to 7 May 2014 at Lindholmen Conference Centre.PROMSUS was arranged in collaboration between four partners and with partial financing from the Swedish EnergyAgency.In connection to PROMSUS an open seminar was arranged by European Enterprice Network, together with thePROMSUS group and Lighthouse, at the Swedish Sea Rescue Society in Långedrag, Gothenburg.

Per Alvfors KTH Royal Institute of TechnologyKarin Andersson ChalmersTommy Björkqvist TBAB TechnologyJoakim Bomanson ScandiNAOS ABSelma Brynolf ChalmersDinko Chakarov ChalmersJason Chesko MethanexRoland Clift CES SurreyDaniel Cohn MITIngemar Denbratt ChalmersJoanne Ellis SSPAPer Fagerlund ScandiNAOS ABErik Fridell IVL Swedish Environmental Research

InstituteKristina Furubacke WärtsiläRikard Gebart Luleå University of TechnologyMaria Grahn ChalmersBjörn Hall Stena MetallJohn B Hansen Haldor Topsoe

Lennart Haraldson WärtsiläSjur Haugen Statoil Fuel & Retail ASBengt Johansson Lund UniversityPatrik Klintbom Volvo GroupKlaus Lackner Columbia UniversityIngvar Landälv Luleå University of TechnologyKarin Pettersson ChalmersLars J Pettersson KTH Royal Institute of TechnologyG. K Surya Prakash USCBengt Ramne ScandiNAOS ABWolfgang Seuser Methanol Market Services AsiaPer Stefenson Stena TeknikThomas Stenhede WärtsiläHenrik Thunman ChalmersK-C Tran Carbon Recycling InternationalSören Udd Swedish Internal Combustion Engine

ConsortiumAlberto Varone IASS

PROMSUS participants: