Methanol: a future transport fuel based on hydrogen and ... · PDF fileMethanol: a future...

Methanol: a future transport fuel based on hydrogen and

carbon dioxide?

Methanol Production and use from a life-cycle perspective

Enrique Ipiñazar. TECNALIA

STOA - EU Parliament - Brussels, October 17th 2013

1.- INDUSTRIAL METHANOL PRODUCTION EXISTING PROCESSES 2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION . 3.- OTHER POTENTIAL USES OF CO2 AS RAW MATERIAL 4.- ECONOMICAL, SOCIAL AND ENVIRONMENTAL PERSPECTIVES OF THE METHANOL PRODUCTION AND TRANSPORT USE. 5.- CONCLUSIONS

CONTENT OF THIS PRESENTATION

1.- INDUSTRIAL METHANOL PRODUCTION EXISTING PROCESSES

Up to the 1920´s wood was the only source for methanol, as byproduct in the charcoal production. Beginning in the 1920, the production of methanol from syngas on an industrial scale was introduced by BASF in Germany.

Whereas coal was initially used as a feedstock for the syngas, natural gas became the preferred feedstock after the World War II.

TWO STEPS: 1. Methane steam reforming to syngas CH4 + H2O ⇔ CO + 3 H2 2. Syngas WGS to methanol

CO + 2H2 ⇔ CH3OH CO2 + CO + 5H2 ⇔ 2CH3OH + H2O

Methanol production process from fossil fuel based syngas (Globally production rate: over 40 millions Tn/year) .

Methanol synthesis is an exothermic reaction (-21.7 kcal mol–1) and control of the process temperature is important to avoid rapid deactivation of the catalyst (Olah, G.A. 2009).

Coal GasificationSteam reforming

ATRHydrogasification

DR

Syngas(H2 + CO+ CO2)

Biomass

Methanol productionprocess

Heavier feedstocks: - Coal - Heavy oil - Oil refining residues - Biomass - Biogas

Process to obtain a syngas - Gasification: it is a thermal process in which organic materials are converted in CO and H2, the syngas. - Autothermal reforming, ATR: a combination of steam reforming and partial oxidation, the result is a syngas with an ideal ratio of hydrogen. - Steam reforming: light hydrocarbons can be reformed at high temperatures (800-1.000ºC) and low pressures (typically <25bar) in the presence of a nickel-based catalyst. This reaction is very endothermic - Dry Reforming, DR: the reforming process is with CO2. Very endothermic reaction. Appropriate for feedstocks with CO2, such as biogas. - Hydrogasification: also named the Hynol process, from the Brookhaven National Laboratory (USA), is a process for converting biomass to syngas at high-temperature (1.000°C) and under moderate pressure (~30bar).



Methanol from natural gas or coal in Europe?

• The most secure gas supplies for Europe come from the Norwegian gas deposits connected by pipelines to the EU, but these are expected to peak by 2015/2016 and to start declining by 2030, according to simulations based on near-by fields.

• With regard to coal, simulations based on the production curves of coal mines worldwide, suggested that coal production reached its peak in 2011 and will decrease by 50% in 2050, even accounting for important new deposits still to be developed in regions such as Alaska and Siberia. Reserve estimates also tend to underestimate the effects of policies seeking to substitute oil derivates by other fuels, for example the use of liquefied coal in military and civilian aviation.


Source: Own elaboration based on data from Nexant, Chemsystems

0%5%

10%15%

20%25%

30%35%

Olefins

Gasoline blending

Biodiesel

DME

Acetic Acid

MTBE

Form aldehyde

Others

4%

6%

4%

10%

10%

11%

31%

24%

Methanol consumption world-wide, by application, 2011

http://www.chemsystems.com/about/cs/news/items/SBA12 Methanol.cfm

2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION

0

5.000.000

10.000.000

15.000.000

20.000.000

25.000.000

30.000.000

35.000.000

1960196219641966196819701972197419761978198019821984198619881990199219941996199820002002200420062008

Global emissions of carbon dioxide (CO2) – the main cause of global warming – increased by 3% in 2011, reaching an all-time high of 34 billion tonnes in 2011. The top 5 emitters are China (share 29%), the United States (16%), the European Union (EU27) (11%), India (6%) and the Russian Federation (5%), followed by Japan (4%). * Fossil fuel combustion accounts for about 90% of total global CO2 emissions, excluding those from forest fires and the use of wood fuel (EDGAR 4.2, JRC/PBL, 2011).

Golbal emission of CO2 along the last 40 years Source: Banco Mundial

* Source: Trends in global CO2 emissions; 2013 Report © PBL Netherlands Environmental Assessment Agency


Electricity and heat production 1,006.6 million tons Other energy sector own use 160.7 million tons Manufacturing industry and construction

467.9 million tons

Transport

of which: road

811.4 million tons

760.4 mt Other sectors 610.1 million tons

Source: Own elaboration based on data from IEA 2012

Sources of CO2 emissions in Europe

2.- CO2 AS RAW MATERIAL TO METHANOL

• Annual CO2 emissions from fossil fuel combustion and cement production were 8.3 [7.6 to 9.0] GtC12 yr–1 averaged over 2002–2011 (high confidence) and were 9.5 [8.7 to 10.3] GtC yr–1 in 2011, 54% above the 1990 level. Annual net CO2 emissions from anthropogenic land use change were 0.9 [0.1 to 1.7] GtC yr–1 on average during 2002 to 2011 (medium confidence).

• From 1750 to 2011, CO2 emissions from fossil fuel combustion and cement production have released 365 [335 to 395] GtC to the atmosphere, while deforestation and other land use change are estimated to have released 180 [100 to 260] GtC. This results in cumulative anthropogenic emissions of 545 [460 to 630] GtC.

• The maximum production potential of methanol from CO2 capture in Europe can therefore be roughly estimated at 930 million tons / year, which equals 1,173,475 million litres of methanol per year or 3,215 million litres per day, one third more than the present fuel demand of the automotive sector.

Source: IPPC


Overview - process efficiency of CO2 conversion to methanol

Carbon Capture and Storage (CCS) technologies for CO2 capture


PROBED TECHNOLOGIES HIGH ENERGY CONSUMPTION

- PSA - TSA - Amine absorption - Membrane separation

Renewable energy

CO2

Electricity

Electrolysis of waterRenewable

H2

H2 +Synthesis

CH3OH

Use as fuel CCSCO2

CO2 from fossil fuelsburning at power plants

Critical issue: the separation and concentration of CO2 at high volume


Hydrogen sources

1. From hydrocarbons. Hydrogen is co-produced in the reforming of hydrocarbons to produce fuels.

2. From methane: Methane can be decomposed into carbon and hydrogen at high temperature.

3. From WATER: Electrolysis of water produces oxygen and hydrogen. The power necessary for the process can be obtained from renewable sources, like solar or eolic.

CO2 sources

1. Atmospheric CO2 , extracted from air

2. Post-combustion CO2 , may be extracted by a series of known separation processes

3. Biogas from anaerobic digestion, separating the CO2 from the CH4

2.- CO2 AS RAW MATERIAL TO METHANOL

21 23

40

17

29

1

2008 2009 2010 2011 2012 2013

Nº of patents 2008 - 2013

0

10

20

30

40

50

60

CN JP US DE RU CH GB SE DK KR PL TW FR NL RO

Nº of patents by country 2008 - 2013

Number of patents on CO2 conversion to methanol 2008 – 2013


Source: Galindo et al 2007


The “solarisation” of methanol production

Source: Adapted from Schmitz et al 2010


Las emisiones de dióxido de carbono son las que provienen de la combustión de combustibles fósiles y de la fabricación del cemento. Incluyen el dióxido de carbono producido durante el consumo de combustibles sólidos, líquidos Y gaseosos. En cifras, suponen mas del 78 % del origen de las emisiones mundiales.

Parameter Absorption Adsorption Membrane Cryogenic

Energy requirements 4-6 MJ/kgCO2

2-3 MJ/kgCO2 0.5-6 MJ/kgCO2 6-10 MJ/kgCO2

CO2 recovery 90-98% 80-95% 80-90% >95%

Source: Compiled by Mondal et al 2012 from previous studies

Energy requirements and CO2 recovery levels for carbon capture techniques

Slurry reactor

Operation conditions 210-250 ºC

1-30 bar H2/CO = 2

Highly exothermic reaction!!!

Comercial catalyst Co (15-30%)

Ru, Pt Al2O3


FISCHER- TROPSCH SYNTHESIS


Another processes for methanol production

Electrochemical production: CO2 + H2O + 6H+ + 6e- CH3OH At room temperature Renewable source of electricity can be used Scale-up is relatively simple, compact design Low energetic efficiency Low specific productivity

Enzymatic conversion Involves the use of enzymes and microorganisms as catalyst Ambient temperature and pressure High selectivity and specificity

Dave, B.C., 2008


UNITED STATES

Department of Electrical Engineering, Materials Research Institute. The Pennsylvania State University.

● High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels. Oomman K. Varghese, Maggie Paulose, Thomas J. LaTempa, and Craig A. Grimes. 2009

Depiction of cocatalyst loaded flow-through nanotube array membrane for high rate photocatalytic conversion of CO2 and

water vapor into hydrocarbon fuels.

PATENT: WO2010080703 (A2)

Depiction of sunlight-driven photocatalytic carbon dioxide conversion to hydrocarbon fuels using nitrogen-doped titania nanotube arrays surface-loaded with Cu and/or Pt cocatalyst nanoparticles.

3.- OTHER POTENTIAL USES OF CO2 AS RAW MATERIAL.

DIRECT CO2 VALORIZATION AND INDUSTRIAL USES

CO2 Food and Beverage: • Meat mixing • Beverage carbonatation • Cryogenic freezing and cooling • Greenhouse growing

Healthcare: • Meat mixing

Oil & gas industry: • Enhanced oil &gas recovery Pulp & Paper:

• Ph control • Washing pulp process

Waste water treatment: • Ph control

Welding and metal fabrication: • Inert atmosphere

Welding and metal fabrication: • Inert atmosphere


Schematic presentation of CO2 capture by algae and conversion into biofuels

Source: Adapted from Kumar et al 2011


Products from CO2 hydrogenation

Source: Wang 2011

3.- OTHER POTENTIAL USES OF CO2 AS RAW MATERIAL

Biomass (wastes, different crops, manure, Lignine, fats…)

CO2 from various sources H2 from water with renewable energy

Thermochemical hydrogenation Biotechnology Synthesis with syngas

Biodiesel Bioethanol

Biomethane

Synthetic biofuels (DME, Methanol, )

Chemicals and polymers (Commodities)

Fertilizers

BIOECONOMY CONCEPT

Organic acids and extracts (High added value)


0 50.000 100.000 150.000 200.000 250.000 300.000 350.000 400.000 450.000

Bio-PE

Bio-PET

PLA

PHA

Polyesters

Biodegradable…

Bio-PVC

Pio-PA

Regenerated…

PLA-Blends

Bio-PP

Bio-PC

Others

450.000

290.000

216.000

147.100

143.500

124.800

120.000

75.000

36.000

35.000

30.000

20.000

22.300

Tonnes/year by 2015

EUROPEAN BIOPOLYMER PRODUCTION CAPACITY

Source: Own elaboration based on data from European Plastics

4.- ECONOMICAL, SOCIAL AND ENVIRONMENTAL PERSPECTIVES OF THE METHANOL PRODUCTION AND USE.

000

001

001

002

002

003

003

004

004

Methanol fromcoal

Syngas fromnatural gas

Biomass (totallife cycle)

Flue gas CO2 fromatmosphere

CO2 emissions (kg CO2 / kg MeOH)

Source: Own elaboration based on data collected by Galindo et al 2007

0

10

20

30

40

50

60

70

80

Natural gas Coal Biomass ConcentratedCO2

Ambient CO2

Energy efficiency of methanol production (%), ranges

low

high

Source: Own elaboration based on data collected by Bromberg et al 2010, Galindo 2007 and IRENA 2013

The economics, as well as the energy balance of CO2 capture and methanol production depend to a large degree on the technology choices made and the components, which form a rather complex system


Source: http://www.ineos.com/businesses/INEOS-Paraform/Markets/

Methanol market prices 2007 – 2013

CO2 Source Cost (€/t)

Natural gas 75-250

Coal 150-300

CO2 capture from flue gas 500 - 900

Wood 160 -940

Waste 200 - 500

Source: Own elaboration based on IRENA 2013

Costs of methanol production by source

http://www.ineos.com/businesses/INEOS-Paraform/Markets/




George Olah methanol plant 2012, Iceland

(*)directly blended with gasoline according to the EU/EEA fuel quality directive

(up to 3%) *

geothermal power plant

Production capacity: 5 million liters per year, recycling about 4.500 tons of CO2 per year

Emission to Liquid (ETL technology) patented by CRI

five megawatts of power generation capacity equivalent per year

Iceland’s total potential for producing methanol stand at 350 million liters of methanol a year, which is sufficient to substitute gasoline within the small country (Kauw 2012).


Source: http://www.aspo2012.at/wp-content/uploads/2012/06/Pengg_aspo2012.pdf,

http://www.aspo2012.at/wp-content/uploads/2012/06/Pengg_aspo2012.pdf






Algenol in the US and Pond Biofuel in Canada, produce biofuels, and not methanol, as the final product.

5.- CONCLUSIONS

1.- First conclusions from this interim report indicate that the wide-spread use of methanol in Europe would necessarily have to be based on CO2 as a primary energy source, since secure access to fossil fuel reserves such as coal or gas at affordable prices in not necessarily guaranteed. The main challenge therefore consists in developing efficient processes for capturing CO2 and turning it into methanol, preferably without the need for adding hydrogen. Although hydrogenation is presently the preferred option for this process, it is not an optimum solution, as additional energy input is required and renewable sources are not likely to meet this additional demand for transport purposes. Attention should therefore be paid to alternative processes for directly converting CO2 into methanol, but those processes are in the phase of early research and require, for the moment, scarce catalyst materials. 2.- Several questions affects the potential use of the methanol to become a future transport fuel: How will CO2 emissions evolve over time and will there be a secure and environmentally sound supply of CO2 for conversion into methanol in the longer-term future? Will the new technologies for capturing CO2 and turning it into methanol increase their energy efficiency balances to make them economically viable and by when will they be commercially available? Some challenges still have to be faced:

building a transport infrastructure (location, cost): the distance between CO2 capture and storage facilities will be decisive in terms of costs;

uncertainties on the price of CO2 emission allowances in the long-term. In addition to incentive mechanisms, the market must have a high CO2 allowance price;

the competition for access to CO2 storage sites

5.- CONCLUSIONS

3.- Supply of water as Hydrogen source and energy renewables sources remain the most essential factors for methanol production from CO2. 4.- The extension of the Bioeconomy (industrial biorefinery processes and large use of bioproducts) could jeopardize the methanol as future transport fuel.

Methanol: a future transport fuel based on hydrogen and

carbon dioxide?

Methanol Production and use from a life-cycle perspective

Enrique Ipiñazar. TECNALIA

STOA - EU Parliament - Brussels, October 17th 2013

THANK YOU VERY MUCH FOR YOUR ATTENTION!

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