Jeffrey J. Siirola Purdue University Carnegie Mellon University

Driven in previous decades by materials substitution

Products derived mostly from methane, ethane, propane, aromatics – in turn derived from petroleum and natural gas

Likely driven in the future by GDP growth Supply/demand displacements have affected the

relative cost and availability of some raw materials – leading to the consideration of alternatives

Region

2000 Pop,M pcGDP,k$

2025 Pop,M pcGDP,k$

2050 Pop,M pcGDP,k$

North America 306 30.6 370 40 440 50

Latin America 517 6.7 700 20 820 35

Europe 727 14.7 710 30 660 40

Africa 799 2.0 1260 12 1800 25

Asia 3716 3.6 4760 20 5310 35

World 6065 6.3 7800 20 9030 33

Region

2000 Prod

2000-25 Growth New Plant %Tot

2025-50 Growth New Plant %Tot

North America 1.0 0.6 5 0.8 5

Latin America 0.4 1.1 9 1.6 10

Europe 1.1 1.1 9 0.5 4

Africa 0.2 1.5 12 3.2 21

Asia 1.4 8.2 65 9.3 60

World 4.1 12.6 15.4

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

Environmental Protection Health and Safety Energy Efficiency Product Stewardship Corporate Citizenship Triple Bottom Line Renewable Energy Water Management Biomass Feedstocks National Security Climate Change

Industrial Ecology Life Cycle Analysis Green Chemistry Benign by Design Waste Minimization Watershed Protection Pollution Prevention Low Energy Separations Carbon Trading Clean Products Systems Analysis

Availability Accessibility Concentration Cost of extraction (impact, resources) Competition for material Alternatives "Close" in chemical or physical structure "Close" in oxidation state

-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

Met

hane

Eth

ane

Eth

ylen

e, P

olye

thyl

ene

Nat

ural

Gas

Oil

Coa

l C

arbo

hydr

ates

Pol

ysty

rene

, Pol

yvin

ylch

lorid

e

Pol

yest

er

Ace

tic A

cid

Car

bon

Dio

xide

Car

bon

Mon

oxid

e

Met

hano

l, E

than

ol

Ace

tone

E

thyl

ene

Gly

col,

Eth

yl A

ceta

te

Gly

cerin

, Phe

nol

Lim

esto

ne

Ene

rgy

of F

orm

atio

n

-4 -2 0 +2 +4 +4 (salt) Oxidation State

Recoverable Gas Reserves – 95 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) ◦ Fossil Fuel Consumption – 7.0 GTC/yr ◦ Organic Chemical Production – 0.3 GTC/yr

Atmospheric CO2 (385ppmv) – 750 GTC Estimated Oceanic Inorganic Carbon (30ppm) –

40000 GTC Estimated Limestone/Dolomite/Chalk –

100000000 GTC

Met

hane

Eth

ane

Eth

ylen

e, P

olye

thyl

ene

Nat

ural

Gas

Oil

Coa

l

Car

bohy

drat

es

Pol

ysty

rene

, Pol

yvin

ylch

lorid

e

Pol

yest

er

Ace

tic A

cid

Car

bon

Dio

xide

Car

bon

Mon

oxid

e

Car

bona

te

Met

hano

l, E

than

ol

Ace

tone

E

thyl

ene

Gly

col,

Eth

yl A

ceta

te

Gly

cerin

, Phe

nol

Con

dens

ate

Pro

pane

Lim

esto

ne

Gas

olin

e

The most abundant (carbonate)? The one for which a "renewable" process exists for part

of the required endothermic oxidation state change (atmospheric carbon dioxide via biomass)?

The one likely to co-produce the most energy in addition to final product (natural gas)?

The one likely least contaminated (methane or condensate)?

The one most similar in molecular weight or structure (oil or perhaps biomass)?

A compromise: abundant, close oxidation state, easily removed contaminants, and generally dry (coal)?

As methane, condensate, and light crude become depleted, feedstocks for both transportation fuels and chemicals will become heavier and higher oxidation state

Hydrogen will be required to reduce these feedstocks ◦ If derived as at present from steam reforming, will result in significant

additional carbon dioxide production ◦ Unless derived from solar or nuclear water-splitting

Processes will become net endothermic Reaction energy and separation/purification energy both to be supplied

from utilities

Process industries become much more energy-intensive Greater role for heat integration, multi-effect operation, low-energy

separations, process intensification technologies, etc.

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 carbonate or CO2 (via biomass) as the raw material for most of the organic chemistry industry ◦ But, the same might not necessarily be true for fuels,

especially if CO2 capture is not feasible or practical

Quads Percent GTC

Approximately 1/3 transportation, 1/3 electricity, 1/3 everything else (industrial, home heating, etc.)

Oil 150 40 3.5

Natural Gas 85 22 1.2

Coal 88 23 2.3

Nuclear 25 7

Hydro 27 7

Solar 3 1

Region 2000 2025 2050

North America 90 100 120

Latin America 35 80 150

Europe 110 110 130

Africa 15 60 200

Asia 135 450 900

World 385 800 1500

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 ◦ Or more, if energy-rich (carbon-lean) methane

exhausted ◦ Or more, if synthetic fuels are derived from energy-lean

coal or biomass

At 395ppm, 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 soil carbon and to terrestrial biomass inventory (including impact of changing agricultural and land management practices)

The balance results in ever increasing atmospheric CO2 concentrations (+2ppm/yr)

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

Environmental protection measures of unprecedented magnitude may be mandated

Carbon Dioxide Capture Carbon Dioxide Storage Reduce Carbon Dioxide Production Offset Carbon Dioxide Production

Capture from low partial pressure point sources – fluegas ◦ Alcoholamines ◦ Chilled ammonia ◦ Caustic or lime ◦ Carbonate ◦ Zeolite adsorption ◦ Active transport membranes ◦ Anti-sublimation

Capture from high partial pressure point sources – gasifiers ◦ Rectisol ◦ Selexol ◦ Metal oxides

Collect from sources without nitrogen ◦ Oxygen-fired furnaces, kilns, or turbines (oxyfuel)

Capture from mobile sources ◦ Lithium hydroxide ◦ Polymer amines ◦ Molecular sieves

Collect from atmosphere by scrubbing ◦ Caustic ◦ Anion exchange resins ◦ Optimized reactive sorbent

Collect from atmosphere by growing biomass ◦ Cultivated crops, plantation forest, algae ponds ◦ Natural aquatic and terrestrial vegetation and forests

Geologic (as pressurized gas, supercritical liquid, or carbonic acid; +4 oxidation state) ◦ Porous capped rock (with or without oil recovery) ◦ Coal beds (with or without methane displacement) ◦ Deep saline aquifer

Oceanic (+4 oxidation state) ◦ Ocean disposal (as carbonic acid) ◦ Deep ocean disposal with hydrate formation ◦ Ocean disposal with limestone neutralization (as

bicarbonate solution)

Land disposal as carbonate salt (+4 oxidation state) ◦ Reaction with silicate

Ocean sinking of biomass (0 oxidation state) ◦ Fertilized ocean (iron or nitrogen) ◦ Cultivated terrestrial biomass (crops, grasses, trees, algae) ◦ Uncultivated terrestrial biomass

Land burial of biomass (0 oxidation state) ◦ Terrestrial burial of cultivated biomass and residues ◦ Terrestrial burial of uncultivated biomass ◦ Pyrolysis and separate disposition of liquors and biochar

Land burial of recovered biological and chemical products ◦ Used paper and lumber products ◦ Municipal solid waste ◦ Scrap or recovered chemical products (e.g., polymers)

Post-combustion (low partial pressure, strength, purity, and stability of sorbent) ◦ Chemsorption (hydroxides, amines, carbonates) ◦ Physical sorption (alcohols) ◦ Phase change (anti-sublimation) ◦ Membrane

Pre-combustion (gasification capital) Oxy-combustion (air separation expense)

Energy required to recover CO2 and regenerate

sorbent

Enhanced oil recovery Coalbed methane displacement Depleted reservoirs Saline aquifers Ocean disposal (without or with neutralization) Pipeline transportation network Leak monitoring and mitigation

Compression and injection energy

Flue Gas With 90% CO2

Removal Stripper

Flue Gas In

Rich Solvent

CO2 for Transport & Storage

LP Steam

Absorber

Lean Solvent

Use 30% of power plant output

35

Reduce energy usage ◦ Produce less product (change product portfolio) ◦ Decrease energy use per unit of production (process

improvement) ◦ Recover and reuse energy (process intensification and

heat integration)

Switch to a more energy-intense fossil source for fuel and feedstock ◦ Switch from oil to gas ◦ Switch from coal to gas

Biomass ◦ Growth depends on latitude and rainfall (and soil) ◦ Land competition with agricultural use ◦ Low energy density – high transportation costs

Solar (photovoltaic, solar thermal, wind, etc) ◦ Low source intensity – high capital costs ◦ Variable availability

Nuclear ◦ No experience with nuclear process heat ◦ Shutdowns for refueling ◦ Siting concerns

Fuel swapping (natural gas for coal) Conversion to non-fossil energy sources

(nuclear, solar, or biomass) Reduce energy requirements ◦ Use less energy-intensive chemistry/unit operations ◦ Increase heat and power integration ◦ Operate processes with additional objective to

minimize energy consumption

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Energy conservation ◦ Easier to justify with expansions rather than retrofits ◦ Equipment capital costs rise linearly with energy costs

Fuel switching ◦ Limited gas availability and gas pipeline capacity ◦ Coal boiler derating when fired with gas ◦ Relocation to inexpensive stranded gas results in

expensive product transportation costs

Most plants do not monitor energy consumption on an individual unit operations basis, but only total plant usage for accounting purposes

Processes may be designed for energy efficiency, but do not include degrees of freedom and manipulated variables to minimize energy utilization during operations

Schemes control for desired throughput and product fitness-for-use attributes (composition, purity, color, etc.), but use utilities (energy) to achieve these goals and to reject disturbances

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The same is also true for many other sustainability dimensions ◦ Environmental impact minimization ◦ Raw material and other resource use efficiency ◦ Customer and stakeholder value ◦ Health and safety ◦ Climate change

We consider sustainability attributes when

selecting and optimizing among alternatives during design, but rarely control for these same objectives during operations

Intensified application of manufacturing intelligence using advanced sensors, modeling, and very large scale simulation

Encompasses the technology, interoperability, operational practice, and shared business infrastructure on which manufacturing intelligence can be generated and applied to multiple sustainability objectives including economic, energy, environment, health, safety and other performance metrics

View sustainability as objectives to be optimized rather than simply as regulatory constraints

Many more sensors and monitors Massive computing infrastructure Real-time error detection and data reconciliation

and very large scale dynamic simulation Engineering modifications to increase

operational degrees of freedom Optimized control of energy consumption,

environmental impact, and other sustainability objectives in addition to production rate, quality, and fitness-for-use product objectives

Monitoring of every individual utility consumption point

Active control of individual tray hydraulics at incipient flood for maximum efficiency

Hard and soft sensors for improved real-time modeling (e.g., Dzyacky flooding predictor based on pressures, temperatures, levels, flow rates)

Natural gas is the fuel that powers most (but not quite all) US chemical and refining processes

Natural gas methane is the feedstock for hydrogen production (for hydrocracking, hydrodesulfurization, and ammonia) and for syngas (for methanol, and its derivatives e.g. MTBE, formaldehyde, and acetic acid)

Natural gas condensate (ethane and propane) was an advantaged raw material via ethylene and propylene to much of the organic chemicals industry (compared to crude-oil-derived naphtha)

Chemicals from methane ◦ Methanol production moves offshore to sources of stranded

gas ◦ MTBE abandoned as gasoline oxygenate ◦ Ammonia moves to Canada ◦ Hydrogen becomes expensive (and low-sulfur diesel at the

pump becomes more expensive than regular gasoline)

Chemicals from condensate and naphtha ◦ Condensate price rises with natural gas (for awhile) ◦ Ethylene price spikes ◦ Propylene price finally rises higher than ethylene

Shut down older cracker capacity Abandon some ethylene derivatives (polyethylene)

and seek C1 routes to others (ethylene glycol, acetaldehyde) as previously done for acetic acid/anhydride)

Abandon polypropylene Seek C1 routes to propylene (MTP) for existing oxo

derivatives and other intermediates currently made from propylene (acrylics, methacrylics, acetone, etc)

Developed process for the large-scale gasification of petcoke, lignite, or coal as source of syngas for C1 chemistries and refinery hydrogen

Flight to off-shore production (to sources of stranded methane and condensate - Persian Gulf)

Bio-based feedstocks (ethylene from sugar-based bioethanol dehydration - Brazil)

Feedstocks from coal gasification and liquefaction (China)

Calls for increased LNG infrastructure Development of directional and horizontal

drilling and hydraulic fracturing technologies (Shale Gas)

Unconventional natural gas (as is coalbed methane, tight sandstone gas, and methane hydrates)

Found in relatively thin shale formations of very low permeability

Economic production enabled by two technological innovations: ◦ Directional drilling ◦ Hydraulic fracturing

Technology and field development encouraged by high natural gas prices

http://upload.wikimedia.org/wikipedia/commons/b/bb/GasDepositDiagram.jpg

Shale gas now reclassified as conventional gas North American conventional gas reserves doubled Price of natural gas (compared to oil) dropped by 80%

Accelerate electric power fuel switching from coal to

natural gas Killed many proposed gasification projects Restored US production of methanol and ammonia Condensate crackers restarted Restored advantaged North American feedstock position

for many organic chemicals

Natural gas replacement for coal as the primary early carbon management technique (source reduction)

Increased deployment of highly efficient Natural Gas Combined Cycle plants for electricity production and chemical plant cogeneration

Increased US production and export of chemicals decreasing the trade deficit

For many intermediates, interesting competition between C1 (methane) and C2 (ethane) feedstocks resulting from advances in catalysis, energy efficiency, and process design optimization

Electricity power plant fuel switching could dominate the rate of shale gas development

Amount of gas producible from shale formations might be less than predicted

Additional shale formations might be more expensive to produce than first experiences suggest

Some shale formations might be geologically inappropriate for development (e.g. shallow formations near groundwater supplies)

Production technologies (especially hydraulic fracturing) might have unintended environmental consequences leading to political or regulatory restrictions

Depends on how long shale gas remains plentiful and whether it is wet or dry

If plentiful and wet, then the existing North American ethane-based chemical industry infrastructure will remain world-competitive

If plentiful but dry, new C1 chemistries will emerge, but based on methane steam reforming syngas

If successfully extended to oil shale development, the role for naphtha cracking infrastructure may be extended

If a great deal of infrastructure is put in place to displace coal by natural gas for electricity production and for institutional and industrial boilers and to otherwise expand the use of methane for chemical production,

But natural gas becomes less economically advantaged compared to coal…

Then coal gasification may once again return, But if so, most likely only to make Synthetic Natural Gas

(SNG)! ◦ With the corresponding carbon dioxide captured and sequestered