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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).
1.- INDUSTRIAL METHANOL PRODUCTION EXISTING PROCESSES
1.- INDUSTRIAL METHANOL PRODUCTION EXISTING PROCESSES
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.
1.- INDUSTRIAL METHANOL PRODUCTION EXISTING PROCESSES
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
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
2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION
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
2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION
Overview - process efficiency of CO2 conversion to methanol
Carbon Capture and Storage (CCS) technologies for CO2 capture
2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION
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
2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION
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
2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION
Source: Galindo et al 2007
2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION
The “solarisation” of methanol production
Source: Adapted from Schmitz et al 2010
2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION
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
2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION
FISCHER- TROPSCH SYNTHESIS
2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION
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
2.- CO2 AS RAW MATERIAL FOR METHANOL PRODUCTION
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
3.- OTHER POTENTIAL USES OF CO2 AS RAW MATERIAL.
Schematic presentation of CO2 capture by algae and conversion into biofuels
Source: Adapted from Kumar et al 2011
3.- OTHER POTENTIAL USES OF CO2 AS RAW MATERIAL.
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)
3.- OTHER POTENTIAL USES OF CO2 AS RAW MATERIAL.
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
4.- ECONOMICAL, SOCIAL AND ENVIRONMENTAL PERSPECTIVES OF THE METHANOL PRODUCTION AND USE.
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
4.- ECONOMICAL, SOCIAL AND ENVIRONMENTAL PERSPECTIVES OF THE METHANOL PRODUCTION AND USE.
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).
4.- ECONOMICAL, SOCIAL AND ENVIRONMENTAL PERSPECTIVES OF THE METHANOL PRODUCTION AND USE.
Source: http://www.aspo2012.at/wp-content/uploads/2012/06/Pengg_aspo2012.pdf,
4.- ECONOMICAL, SOCIAL AND ENVIRONMENTAL PERSPECTIVES OF THE METHANOL PRODUCTION AND USE.
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!