sustainability siirola apr 2007

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Sustainability in the Chemical and Energy Industries: 

Sustainability in the Chemical and Energy Industries Jeffrey J. Siirola Eastman Chemical Company Kingsport, TN 37662

Sustainable Chemical Processes: 

Sustainable Chemical Processes Attempt to satisfy… Investor demand for unprecedented capital productivity Social demand for low present and future environmental impact While producing… Highest quality products Minimum use of raw material Minimum use of energy Minimum waste In an ethical and socially responsible manner

Chemical Industry Growth: 

Chemical Industry Growth Driven in previous decades by materials substitution Products derived mostly from methane, ethane, propane, aromatics Likely driven in the future by GDP growth Supply/demand displacements are beginning to affect the relative cost and availability of some raw materials

Population and GDP Estimates: 

Population and GDP Estimates

Process Industry Growth Current North America = 1.0: 

Process Industry Growth Current North America = 1.0

Medium Term Economic Trends: 

Medium Term Economic Trends Much slower growth in the developed world Accelerating growth in the developing world World population stabilizing at 9-10 billion 6-7 X world GDP growth over next 50 or so years (in constant dollars) 5-6 X existing production capacity for most commodities (steel, chemicals, lumber, etc.) 3.5 X increase in energy demand 7X increase in electricity demand

Is such a future "sustainable"?: 

Is such a future "sustainable"?

Raw Materials: 

Raw Materials

Raw Material Selection Characteristics: 

Raw Material Selection Characteristics Availability Accessability Concentration Cost of extraction (impact, resources) Competition for material Alternatives "Close" in chemical or physical structure "Close" in oxidation state

"Oxidation States" of Carbon: 

"Oxidation States" of Carbon -4 Methane -2 Hydrocarbons, Alcohols, Oil -1 Aromatics, Lipids 0 Carbohydrates, Coal +2 Carbon Monoxide +4 Carbon Dioxide -2 – -0.5 Most polymers -1.5 – 0 Most oxygenated organics

Matching Raw Material and Desired Product Oxidation States: 

Matching Raw Material and Desired Product Oxidation States Methane Ethane Ethylene, Polyethylene Natural Gas Oil Coal Carbohydrates Polystyrene, Polyvinylchloride Polyester Acetic Acid Carbon Dioxide Carbon Monoxide Methanol, Ethanol Acetone Ethylene Glycol, Ethyl Acetate Glycerin, Phenol Limestone

Energy and Oxidation State Carbon: 

Energy and Oxidation State Carbon Energy of Formation -4 -2 0 +2 +4 +4 (salt) Oxidation State

Global Reduced Carbon: 

Global Reduced Carbon Recoverable Gas Reserves – 75 GTC Recoverable Oil Reserves – 120 GTC Recoverable Coal – 925 GTC Estimated Oil Shale – 225 GTC Estimated Tar Sands – 250 GTC Estimated Remaining Fossil (at future higher price / yet-to-be-developed technology) – 2500 GTC Possible Methane Hydrates – ????? GTC Terrestrial Biomass – 500 GTC Peat and Soil Carbon – 2000 GTC Annual Terrestrial Biomass Production – 60 GTC/yr (more than half in tropical forest and tropical savanna) Organic Chemical Production – 0.3 GTC/yr

Global Oxidized Carbon: 

Global Oxidized Carbon Atmospheric CO2 (380ppmv) – 750 GTC Estimated Oceanic Inorganic Carbon (30ppm) – 40000 GTC Estimated Limestone/Dolomite/Chalk – 100000000 GTC

If Carbon Raw Material is a Lower Oxidation State than the Desired Product: 

If Carbon Raw Material is a Lower Oxidation State than the Desired Product Direct or indirect partial oxidation Readily available, inexpensive ultimate oxidant Exothermic, favorable chemical equilibria Possible selectivity and purification issues Disproportionation coproducing hydrogen Endothermic, sometimes high temperature Generally good selectivity OK if corresponding coproduct H2 needed locally Carbonylation chemistry CO overoxidation can be readily reversed

If Carbon Raw Material is a Higher Oxidation State than the Desired Product: 

If Carbon Raw Material is a Higher Oxidation State than the Desired Product Reducing agent typically hydrogen Hydrogen production and reduction reactions net endothermic Approximately athermic disproportionation of intermediate oxidation state sometimes possible, generally coproducing CO2 Solar photosynthetic reduction of CO2 (coproducing O2)

Industrial Hydrogen Production: 

Industrial Hydrogen Production To make a mole of H2, either water is split or a carbon is oxidized two states (or two carbons oxidized one state each) Electrolysis/thermolysis H2O = H2 + ½ O2 Steam reforming methane CH4 + 2 H20 = 4 H2 + CO2 Coal/biomass gasification C + H2O = H2 + CO C(H2O) = H2 + CO Water gas shift CO + H2O = H2 + CO2 Cracking -CH2CH2- = H2 + -CH=CH-

Matching Raw Material and Product Oxidation States / Energy: 

Matching Raw Material and Product Oxidation States / Energy Methane Ethane Ethylene, Polyethylene Natural Gas Oil Coal Carbohydrates Polystyrene, Polyvinylchloride Polyester Acetic Acid Carbon Dioxide Carbon Monoxide Carbonate Methanol, Ethanol Acetone Ethylene Glycol, Ethyl Acetate Glycerin, Phenol Condensate Propane Limestone Gasoline

Which is the sustainable raw material? : 

Which is the sustainable raw material? The most abundant (carbonate)? The one for which a "natural" process exists for part of the required endothermic oxidation state change (atmospheric carbon dioxide)? The one likely to require the least additional energy to process into final product (oil)? The one likely to produce energy for export in addition to that required to process into final product (gas)? The one likely least contaminated (methane or condensate)? The one most similar in structure (perhaps biomass)? A compromise: abundant, close oxidation state, easily removed contaminants, generally dry (coal)?

Energy: 

Energy

Current World Energy Consumption Per Year: 

Current World Energy Consumption Per Year Quads Percent GTC Approximately 1/3 transportation, 1/3 electricity, 1/3 everything else (industrial, home heating, etc.)

Fossil Fuel Reserves : 

Fossil Fuel Reserves Recoverable Reserve Life Reserve Life Reserves, @Current @Projected GDP GTC Rate, Yr Growth, Yr

Economic Growth Expectation: 

Economic Growth Expectation World population stabilizing below 10 billion 6-7 X world GDP growth over next 50 or so years 5-6 X existing production capacity for most commodities (steel, chemicals, lumber, etc.) 3.5 X increase in energy demand (7 X increase in electricity demand) Most growth will be in the developing world

Global Energy Demand Quads: 

Global Energy Demand Quads

50-Year Global Energy Demand: 

50-Year Global Energy Demand Total energy demand – 1500 Quads New electricity capacity – 5000 GW One new world-scale 1000 MW powerplant every three days Or 1000 square miles new solar cells per year Clean water for 9 billion people Carbon emissions growing from 7 GTC/yr to 26 GTC/yr More, if methane exhausted More, if synthetic fuels are derived from coal or biomass

What to do with Fossil Fuels: 

What to do with Fossil Fuels Based on present atmospheric oxygen, about 400000 GTC of previously photosynthetic produced biomass from solar energy sank or was buried before it had the chance to reoxidize to CO2, although most has disproportionated We can ignore and not touch them We can use them to make chemical products themselves stable or else reburied at the end of their lives We can burn them for energy (directly or via hydrogen, but in either case with rapid CO2 coproduction) We can add to them by sinking or burying current biomass

Consequences of Continuing Carbon Dioxide Emissions: 

Consequences of Continuing Carbon Dioxide Emissions At 380ppm, 2.2 GTC/yr more carbon dioxide dissolves in the ocean than did at the preindustrial revolution level of 280ppm Currently, about 0.3 GTC/yr is being added to terrestrial biomass due to changing agricultural and land management practices, but net terrestrial biomass is not expected to continue to increase significantly The balance results in ever increasing atmospheric CO2 concentrations

Carbon Dioxide Sequestration: 

Carbon Dioxide Sequestration Limited options for concentrated stationary sources Geologic formations (EOR, CBM, deep well) Saline aquifers Deep ocean Alkaline (silicate) mineral sequestration Enhanced oceanic or terrestrial biomass / soil carbon Fewer options for mobile sources Onboard adsorbents Enhanced oceanic or terrestrial biomass / soil carbon

Can We do it with Biomass?: 

Current Fossil Fuel Consumption – 7 GTC/yr Current Chemical Production – 0.3 GTC/yr Current Cultivated Crop Production – 6 GTC/yr Current energy crop production – 0.02 GTC/yr Annual Terrestrial Biomass Production – 60 GTC/yr Future Energy Requirement (same energy mix) – 26 GTC/yr Future Energy Requirement (from coal or biomass) – 37 GTC/yr Plus significant energy requirement to dehydrate biomass Future Transportation Fuel (carbon content only) – 12 GTC/yr Future Chemical Demand – 1.5 GTC/yr Future Crop Requirement – 9 GTC/yr Can We do it with Biomass?

Sustainability Challenges: 

Sustainability Challenges Even with substantial lifestyle, conservation, and energy efficiency improvements, global energy demand is likely to more than triple within fifty years There is an abundance of fossil fuel sources and they will be exploited especially within developing economies Atmospheric addition of even a few GTC/yr of carbon dioxide is not sustainable In the absence of a sequestration breakthrough, reliance on fossil fuels is not sustainable Photosynthetic biomass is very unlikely to meet a significant portion of the projected long term energy need

Capturing Solar Power: 

Capturing Solar Power Typical biomass growth rate – 400 gC/m2/yr (range 100 (desert scrub) to 1200 (wetlands)) Power density – 0.4 Wt/m2 (assuming no energy for fertilizer, cultivation, irrigation, harvesting, processing, drying, pyrolysis) Average photovoltaic solar cell power density – 20-40 We/m2 (10% module efficiency, urban-desert conditions) Solar thermal concentration with Stirling engine electricity generation is another possibility at 30% efficiency Because of limited arable land, available water, harvesting resources, and foodcrop competition, biomass may not be an optimal method to capture solar energy

Solar Energy Storage Options: 

Solar Energy Storage Options In atmospheric pressure gradients (wind) and terrestrial elevation gradients (hydro) In carbon in the zero oxidation state (biomass or coal) In carbon in other oxidation states (via disproportionation, digestion, fermentation) In other redox systems (batteries) As molecular hydrogen As latent or sensible heat (thermal storage)

The Hydrogen Option: 

The Hydrogen Option Potentially fewer pollutants and no CO2 production at point of use Fuel cell efficiencies potentially higher than Carnot-limited thermal cycles No molecular hydrogen available Very low energy density Very difficult to store Consumer handling issues An energy carrier, not an energy source

Hydrogen Production: 

Hydrogen Production If from reduced carbon, then same amount of CO2 produced as if the carbon were burned, but potential exists for centralized capture and sequestration Could come from solar via (waste) biomass gasification, thermal or photochemical water splitting, or photovoltaic or thermoelectric driven electrolysis

Energy Carriers and Systems: 

Energy Carriers and Systems For stationary applications: electricity, steam, town gas, and DME from coal, natural gas, fuel oil, nuclear, solar, hydrogen Electricity generation and use efficient, but extremely difficult to store Battery or fuel cell backup for small DC systems CO2 sequestration possible from large centralized facilities For mobile (long distance) applications: gasoline/diesel, oil Electricity for constrained routes (railroads) only Hydrogen is also a long term possibility For mobile (urban, frequent acceleration) applications: gasoline/ diesel, alcohols, DME Vehicle mass is a dominant factor Narrow internal combustion engine torque requires transmission Disadvantage offset and energy recovery with hybrid technology Highest energy density (including containment) by far is liquid hydrocarbon Capturing CO2 from light weight mobile applications is very difficult

US Energy Picture: 

US Energy Picture 60% of crude oil is imported 60% of imports are from regions with which the US does not always enjoy friendly relations Presidential goal to replace 75% of crude oil currently imported from the Mid-East with domestically-produced alternatives 9% of current US oil demand Infrastructure requirement equal in size to entire existing US organic chemical industry

Conclusions: 

Conclusions By a factor of 105, most accessible carbon atoms on the earth are in the highest oxidation state However, there is plenty of available carbon in lower oxidation states closer to that of most desired chemical products High availability and the existence of photosynthesis does not argue persuasively for starting from CO2 or carbonate as raw material for most of the organic chemistry industry But, the same might not necessarily be true for the transportation fuels industry, especially if the energy carrier is carbonaceous but onboard CO2 capture is not feasible

Conclusions: 

Conclusions Inexpensive natural gas, condensate, and oil will become depleted With enough capital, can get to any carbon oxidation state from any other, but reducing oxidation state costs energy There will be a shift to higher oxidation state starting materials including coal and biomass for chemical and fuel production, with corresponding increases in CO2 generation Sequestration innovations will be essential

The Chemical Industry: 

The Chemical Industry Most new chemical capacity will be built near the customer (except when the raw material is stranded gas) Some new processes will be built to substitute for declining availability of natural gas, condensate, and aromatics Some new processes will be built implementing new routes to intermediates currently derived from methane, olefins, and aromatics Catalysis, process chemistry, and process engineering innovations will be critical

The Energy Industry: 

The Energy Industry Again, there will be a shift to higher oxidation state starting materials for energy production with corresponding increases in CO2 generation Significant new capacity will be built for synthetic fuels In the long term, solar, nuclear, and geothermal energy will be employed to produce electricity and may be employed to produce hydrogen for fuel use directly or for reaction with atmospheric CO2 to produce a more convenient carbonaceous fuel Within 50 years, the size of the global synthetic fuel infrastructure may very well be more than three times the entire existing petroleum-based fuel infrastructure (over 200 times the entire existing US chemical industry)

Slide41: 

Addendum A Roadmap to Chemical and Energy Sustainability

Sustainability Roadmap Immediate: 

Sustainability Roadmap Immediate 1. Conserve, recover, reuse

Sustainability Roadmap Immediate: 

Sustainability Roadmap Immediate 2. Reevaluate expense/investment optimizations in light of fundamental changes in relative feedstock availability and cost and capital/energy relationships

Sustainability Roadmap Short Term: 

Sustainability Roadmap Short Term 3. For fuels, develop economically justifiable processes to utilize alternative fossil and biological feedstocks. Develop refining modifications as necessary to process feedstocks with alternative characteristics. Develop user (burner, vehicle, distribution, storage, etc) modifications as necessary to adapt to differences experienced by the ultimate consumer.

Sustainability Roadmap Short Term: 

Sustainability Roadmap Short Term 4. For organic chemicals, develop economically justifiable processes to utilize alternative feedstocks. Develop processes to make first-level intermediates from alternative feedstocks. Develop processes to make second-level intermediates from alternative first-level intermediates (from alternative feedstocks).

Sustainability Roadmap Intermediate Term: 

Sustainability Roadmap Intermediate Term 5. For fuels and used organic chemicals that are burned/incinerated at a stationary site, develop, evaluate, and implement alternative processing, combustion, carbon dioxide capture, and carbon dioxide sequestration technologies

Sustainability Roadmap Intermediate Term: 

Sustainability Roadmap Intermediate Term 6. For transportation fuels and dispersed heating fuels, consider stationary conversion of coal or biomass to lower oxidation state carbonaceous energy carriers with resulting coproduct carbon dioxide recovery and sequestration, as above

Sustainability Roadmap Intermediate Term: 

Sustainability Roadmap Intermediate Term 7. For transportation fuels and dispersed heating fuels, consider stationary conversion of carbonaceous materials to non-carbon energy carriers with coproduct carbon dioxide recovery and sequestration, as above

Sustainability Roadmap Intermediate Term: 

Sustainability Roadmap Intermediate Term 8. For carbonaceous energy carriers and dispersed organic chemicals, grow and harvest an equivalent amount of biomass for either feedstock or burial. Develop geographically appropriate species optimized (yield, soil, water, fertilization, cultivation, harvesting, processing requirements (including water recovery), disease and pest resistance, genetic diversity, ecosystem interactions, etc) for this purpose.

Sustainability Roadmap Intermediate Term: 

Sustainability Roadmap Intermediate Term 9. Exploit nuclear (and geothermal) energy for electricity generation and industrial heating uses

Sustainability Roadmap Intermediate Term: 

Sustainability Roadmap Intermediate Term 10. Exploit hydro, wind, and solar photovoltaic for electricity production and solar thermal for electricity production, domestic heating, and industrial heating uses

Sustainability Roadmap Intermediate Term: 

Sustainability Roadmap Intermediate Term 11. Exploit solar or nuclear energy to produce hydrogen to reduce biomass or coal to lower oxidation state forms and to process into carbonaceous fuels

Sustainability Roadmap Intermediate Term: 

Sustainability Roadmap Intermediate Term 12. Exploit solar and nuclear energy chemically or biochemically to reduce carbon dioxide (recovered from carbonaceous burning or coproduct from oxidation state reduction operations) into lower oxidation state forms for sequestration or reuse as carbonaceous energy carriers and organic chemicals

Sustainability Roadmap Long Term: 

Sustainability Roadmap Long Term 13. Develop non-biological atmospheric carbon dioxide extraction and recovery technology with capacity equal to all disperse carbon dioxide emissions from fossil fuel combustion (for transportation or dispersed heating) and from used organic chemicals oxidation (from incineration or biodegradation)

Sustainability Roadmap Long Term: 

Sustainability Roadmap Long Term 14. Convert carbon dioxide extracted from the atmosphere to carbonaceous energy carriers and organic chemicals with water and solar-derived energy (utilizing thermal and/or electrochemical reactions)

Slide56: 

Thank You

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