Chemical Processes of Sustainable and Renewable Energy

Chemical Processes of sustainable and renewable energy
General Contents & Course Structure
1. Aims of this course

2. Background and present status
3. Necessities, ground rules and practice
4. Theory and principles of various energy options
5. Operational limitations of these options
6. Research and developmental challenges
7. Selected examples of various renewable methods
8. Brief presentations of selected topics by students
Prof.K.R. Thampi, Masters 1

Renewable Energy 2013-14

Sustainability!!

Sustainability means having the ability to meet the needs of a

healthy lifestyle for all people in the present without

compromising the needs of future generations.

(C&EN, 85(9), 51, 2007)



Aims of this course

- To introduce the chemistry and chemical engineering concepts of

sustainable and renewable energy vectors

- Provide Notions about the Usage of Energy Sources

As prior knowledge on the use of energy,

-
Important reactions in petroleum processing, coal liquefaction

and hydrogen production from hydrocarbons will be briefly

examined

-
The environmental issues related to CO2 release

-
The concept of CO2 neutral fuels

-
Natural photosynthesis and the artificial mimicking of

photosynthesis

-Thermodynamic principles of energy conversion



Aims of this course (continued)

-
Technical processes involving biomass

-
Bio-gas and liquid bio-fuels,

-
Natural gas usage

-
Various types of solar energy conversion methods and principles

-
Energy storage and low carbon fuels

-
Hydrogen economy, electrolysis and photoelectrolysis of water,

-
Fuel cells and related fuel chemistry

-
Relationship between Economics, Sociology and Science (Debate)



Humanity s Top Ten Problems
for next 50 years

1. ENERGY

2. WATER

3. FOOD

4. ENVIRONMENT

5. POVERTY

6. TERRORISM & WAR

7. DISEASE

8. EDUCATION

9. DEMOCRACY

10. POPULATION

2003 6.3 Billion People
2050 8-10 Billion People
Source Richard Smalley, Energy & Nanotechnology Conference

Rice University, Houston Renewable
May 3, 2003, October 15, 2004.
Energy 2013-14

World primary energy demand



World Energy Demand

2100: 40-50 TW
2050: 25-30 TW
25.00
World Energy Demand
total
20.00
energy gap
~ 14 TW by 2050
15.00 ~ 33 TW by 2100
TW
industrial
10.00
developing
5.00 US 50
World Fuel Mix 2001
ee/fsu oil
0.00 40
1970 1990 2010 2030 *mainly non-sustainable

30
coal
gas
%
20
EIA Intl Energy Outlook 2004
http://www.eia.doe.gov/oiaf/ieo/index.html nucl renew*
10
Hoffert et al Nature 395, 883,1998
Science, 298, 981, 2002
0
85% fossil


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Prof.K.R. Thampi, Masters & 9

European Communities,WW 2006
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Flow of Energy Vectors

Reference Energy System (Flow of Energy Carriers)
Resources Conversion Processes End-Use
Oil Products
Residential/
Oil Refinery T&D Commercial
Thermal
Coal
Heat Plants Residential/
Commercial
Specific
Natural Gas T&D
Industry Thermal
Methanol from
Natural Gas
T&D
Industry Specific
Biofuels
Biomass T&D
Production
CNG
Personal
Transport
Other
Renewables
Aviation
Power Plants T&D
Uranium
Other Transport
Hydrogen
T&D
Production
Coal Non-commercial
Transport Sector
Biomass
GMM has approx. 400 technologies per region T&D: Transport and Distribution
Seite 8
M. Densing, et al., PSI, @ IEW, Prof.K.R. Thampi, Masters 10


Paris, 2013

Personal Transport
Personal Transport Sector Sector

Drivetrains: Internal Combustion Engine Vehicle (ICEV), Advanced ICEV, Hybrid Electric (HEV),
Plug-in (PHEV), Battery Electric (BEV), Hydrogen Fuel Cell with hybridisation (HFCV)
Fuels: conventional liquid (gasoline, diesel); alternatives fuels: natural gas, electricity, hydrogen,
different biofuels; fuel blending (e.g. maximal 10% (Bio-)Methanol into gasoline)
~100 km
Short-Range Car Version
actual drive
Gasoline T&D blend range
Gasoline ICEV
Gasoline
Ethanol (Bio) T&D blend Gas. Adv. ICEV
Retail Station
Gasoline HEV
Bio-Methanol T&D blend
PHEV
Electricity (ELC)
BEV
Methanol T&D blend
Diesel ICEV
Blending Constraints
Diesel Advanced ICEV
Diesel T&D blend
Diesel Retail
Diesel HEV
Station
Biodiesel (FT) T&D blend Hydrogen Hybrid

Hydrogen Retail
ELC HFCV
Bio-Syngas T&D blend

CNG ICEV
Compression
CNG HEV
Natural Gas T&D blend
WEC/PSI (2011): Global Transport Scenarios 2050
Prof.K.R. Thampi, Masters Seite 9
11


Other Surface
OtherTransport and Aviation
Transport SectorsSector

Trucks, buses, other commercial road vehicles, 2-wheel, rail, ships: aggregated by fuel option
Aviation: current + future technology
technologies categorized by
fuelling option, and
engine type
WEC/PSI (2011): Global Transport Scenarios 2050

Prof.K.R. Thampi, Masters Seite 10 12


Fossil: Supply and Security

When Will Production Peak?
World Oil 2037
50
Production gas: beyond oil production peak
40 2016 coal: > 200 yrs
Bbbl/yr
2% demand growth demand exceeds supply

30 ultimate recovery:
3000 Bbbl price increases
20
geo-political restrictions
10
1900 1950 2000 2050 2100

EIA: http://tonto.eia.doe.gov/FTPROOT/
presentations/long_term_supply/index.htm
World Oil Reserves/Consumption

2001
unequal supply
insecure access
OPEC: Venezuela, Iran, Iraq, Kuwait, Qatar, Saudi Arabia,
http://www.eere.energy.gov/vehiclesandfuels/facts/2004/fcvt_fotw336.shtml United Arab Emirates, Algeria, Libya, Nigeria, and Indonesia


This Model of Peak Supply is Now
Changing..

Limits on consumption by the affluent societies, better fuel

efficiency, lower priced alternative fuels and the world's
rapidly urbanizing population

Even in developing countries, economic growth has been

less oil-intensive than was seen in the West during the past
century

The demand for oil as opposed to the supply will reach

its own peak and then decline



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Printed in Belgium Prof.K.R. Thampi, Masters 15

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P - Renewable Energy 2013-14

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Cement Sector CO2 emissions below baseline, low
demand scenario, 2010 2050 (IEA, WBCSD,
2009)



Sense of the energy content

J

kWh

1kWh = approx. 86g of oil (petroleum)

We buy it for 0.2 cents (0.1 + 0.1 for transmission)
as electricity

Required to lift 1225kg 300m

Required to heat 10 L water from 14 to 100C



Making sense of energy

J. Jensen, Energy Storage (1980)



Familiarise with Units

1 joule is:
The IEA/OECD define one toe
to be equal to 41.868 GJ or
1107ergs
11.63 MWh

6.241509741018eV

2.3901104kcal (thermochemical, food, etc.)

9.4782104BTU

2.7778107kWh

2.7778104watt-hour

9.8692103litre-atmosphere



Frequently heard.



Jargon of the trade...

watt (SI unit) W = 1W = 1J/s = 1Nm/s = 1kgm2/s3

Horsepower (boiler) bhp 34.5lb/h 970.3 BTUIT/lb 9.810 657103 W

horsepower (European electrical) hp 75 kpm/s = 736 W

horsepower (Imperial electrical) hp 746 W = 746 W

horsepower (metric) hp 75 m kgf/s = 735.498 75 W

ton of air conditioning 1 t ice melted / 24 h 3 504 W



Energy in a nutshell

J kcal kWh
1 J 238.9 x 10-6 278 x 10-6
1kWh 3.6 x 106 860
1 MWy 31.54 x 1012 7.53 x 109 8760 x 103
1 ton pit coal contains 29.3 x 109 7 x 106 8150
1 m3 NG contains 35.2 x 106 8400 9.8
1 ton crude oil contains 41.9 x 109 107 11650

1 toe = 41.9 GJ
1 kg 235U contains 82 x 1012 19.6 x 109 22.8 x 106


Conventional Fuels/Renewables

1 barrel of oil equivalent (boe) contains approximately 0.146 toe (i.e. 6.841 boe in a toe).

1 t diesel = 1.01 toe

1 m3 diesel = 0.98 toe

1 t petrol = 1.05 toe

1 m3 petrol = 0.86 toe
Ton of oil equivalent:

1 t biodiesel = 0.86 toe
The IEA/OECD define one toe
to be equal to 41.868 GJ or
1 m3 biodiesel = 0.78 toe
11.63 MWh

1 t bioethanol = 0.64 toe

1m3 bioethanol = 0.51 toe

1 MWh = 0.22 toe (assumes 39% thermal to electrical conversion efficiency)

1 MWh = 0.086 toe



Relate to our course and
renewables....

1.51022J: total solar energy that strikes
1 thermochemical calorie = 4.184 J

the face of the Earth each day

1 International Table calorie = 4.1868 J[

5.51024 J: total solar energy that
1 watt hour = 3600 J

strikes the face of the Earth each year

1 kilowatt hour = 3.6106J (or 3.6 MJ)

3.91022 J the estimated energy
contained in the world's fossil fuel
reserves as of 2003

3.341031 J the total energy output of
the Sun each day



Renewable Energy (Technical Values)

Solar energy gap
~ 14 TW by 2050
1 x 105 TW at Earth surface ~ 33 TW by 2100
10,000 TW (technical value)
(1.5 hr sunlight globally = 13 TW-yr)
Wind Biomass
14 TW 5-7 TW
all cultivatable
land not used
for food
Tide/Ocean
Currents
0.7 TW
Hydroelectric
1.2 TW technically feasible
Geothermal 0.6 TW installed capacity
1.9 TW
from Arthur Nozik Prof.K.R. Thampi, Masters 28


Renewable Energy Systems

Important Considerations:

1) Identification of sources appropriate for the target application

2) Energy conversion method to be adopted

3) Direct use or storage? Storage is a key factor in using renewable energies

4) If stored, in which form? (heat, chemical, mechanical, electrical, magnetic)

5) Economics and social aspects

6) Safety and the ease to use

7) Compatibility to the existing technology (gas/liquid vector or solid vector)





An idea on storage capacities..

J. Jensen, Energy Storage (1980)



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M.E. Thesis S. Mernagh, 2013, UCD
Prof.K.R. Thampi, Masters
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Thampi

Role of chemistry and chemical engineering

Today, we are so much dependent on energy for our normal living. Most of our

energy needs are met by fossil fuels. The global climate change requires the stabilization

of atmospheric CO2 levels as a matter of urgency. Given the rising energy demand,

this implies the need for a massive reduction in CO2 emission from fossil fuels.

In the long term, safe, carbon-neutral energy sources will dominate - but such a

transition will be slow. Fossil fuels will continue to play a vital role during this

period, and we must eliminate or reduce the adverse impact that they threaten.

Further, we are confronted with the declining proven oil reserves. Therefore, finding

new energy sources as well as conserving available reserves are of utmost importance.

The latter may be achieved by increasing the energy utilization efficiencies and

chemistry has a key role even in this area. The development of efficient energy conversion
and storage devices are examples. Chemistry and chemical engineering play vital roles in
the development of new materials and device architecture for energy conversion devices.
It also helps the recycling of resources and products to improve the system efficiencies
and acceptability.



Present Status

With the ever increasing demand for affordable energy, our world is rapidly depleting

all the conventional energy resources.

Alternatives are neither technologically mature or economically attractive.

In most cases, the required infrastructure to use other forms of energy is not in place.

Remember that the present society is more tuned to technologies based on liquid fuel

vectors. We may be able to switch over to a gas based vector, but this needs heavy

fresh investment. Apart from coal, which is not eco-frinedly, we are not in a position to

use solid fuels for everything we want to operate.

These are some of the basic constraints you need to keep in mind when working with

renewable energy initiatives.



Look at.

Man made problems related to emission, global
warming and pollution
CO2 as a case study

1. chemical and economic options
2. chemistry of CO2
Energy and chemical building blocks
Gas, liquid and solid energy vectors
Criteria for renewable options in energy


Global CO2 Evolution

In spite of all efforts to curb emissions of polluting gases like

NOx, SOx and CO2, the global emissions of these gases are
increasing steadily


CO2 Mass Balance

Man-made CO2 emission : > 8 gigatons carbon/year (Gtc/yr)
6 Gtc : burning fossil fuels

2 Gtc : deforestation
Natural flow of C : a pprox. 200 Gtc in and out of the
atmosphere every year
But the regular addition of > 8Gtc/year upsets the delicate

equilibrium of the gas distribution in the atmosphere As a
result, the concentration of CO2 i s increasing year after year.
An increase of 0.5% per year corresponds to an annual
increase by about 3.5Gtc. The nature manages to take only 4.5
Gtc of the total 8 Gtc emitted every year.


CO2 and Greenhouse Balance

The increase of man made gases in the earths
atmosphere leads to greenhouse effect, resulting in
global warming. The natural greenhouse effect makes
earth livable by attaining an average 15C temperature.
An increase in temperature away from the natural
setting will create serious consequences to our planet
and its inhabitants.


Influence of CO2 on global temperature



Global Warming Quantified

Global surface temperature has incr eased {approx}0.2C per decade in the
past 30 years.
Comparison of measured sea surface temperatures in the Western Pacific

with paleoclimate data suggests that this critic al ocean region, and
probably the planet as a whole, is approximately as warm now as at th e
Holocene maximum and with in {approx}1C of the maximum temperature
of the past million years.
Thus the global warming of more than {approx}1C, relative to 2000, will
constitute "dangerous" climate chan ge as judged from likely effects on sea
level and extermination of species.
Proceedings of the National Academy of Sciences, DOI:10.1073/pnas.0606291103; J.E. Hansen et al.



Options

1. Minimize emissions: by increasing energy efficiencies;
recycling; co-generation techniques
2. Zero emission options: This option includes using
nuclear, solar, hydro, wind and geothermal methods.
Biomass and its derivatives are also vital and key options
under this category. Examples are alcohols and charcoal
bricks.
3. CO2 control and CO2 chemistry: In here, we can remove
CO2 from the flue gases of the power plants and safely
disposing them in oceans or in land. Another option is to
use CO2 as a feedstock. CO2 may also be used for
enhanced oil recovery, but it may not be a right solution
to fit with the objectives.
4. Grow more hard wood trees and store C in the form of
hard wood trees, timber and furniture. This way it is
possible to store CO2 for several hundred years.


Where does it come from?

Global warming comes from the shift of the heat transfer

equilibrium between Space and the Earth, causing climate
change.

At the equilibrium, where Earth absorbs as much heat from
space as it is emitting to it, the temperatue is stable.



Planetary energy balance

Total blackbody radiation

Total sunlight
absorded by Earth
=
emitted by Earth

Temperature of planet adjusts to level where blackbody radiation

emitted by the Earth equals the sunlight absorbed



Stefan-Boltzmann law

4 2
F = " !T
The image cannot be displayed. Your computer may not have enough memory to open the image, or the image may have been corrupted. Restart your
computer, and then open the file again. If the red x still appears, you may have to delete the image and then insert it again. [W / m ]
The solar flux is 343 W/m2.

Considering reflectivity (albedo) and no atmosphere, only 240 W/m2 is
absorded by Earth (=F).

" T = 254 K = !18C

But it is not the case!

46

So why is the average temperature of the
Earth 15C?

The atmosphere creates the climate we know

and it is regulated by 3 main factors:

Albedo

Atmosphere absorption

Greenhouse effect





Physical mechanism of greenhouse gases

Molecules absorb heat then radiate

isotropically to:
Absorption-emission-
Space
absorption cycle keeps the heat
Earth
near the surface.

Another gas molecule (in Insulates the surface from the
most cases)
cold of space.



Gases in the atmophere

50



Radiative balance change

Rise of greenhouse gases

more energy absorption (IR trapping)

Energy emission not highenough

to counter the imbalance

Rise of the Earth temperature!







Political Will

Reducing Greenhouse effect by reducing gas

emission.

Kyoto Protocol

Reduction of the Carbon
Dioxide of 5% by 2012
compared to 1990



CO2 disposal (i)

The removal of CO2 from power plants in large scale is a !
matured technology and the uses include cooling industry !
(dry ice), and food and beverages. Usually, cold monoethanol-!
amines (MEA) and special polymers are used to chemically !
absorb CO2. When they are heated to >100C, the CO2 will be !
stripped off from the absorber.!
!
Separated CO2 can be dumped in oceans, as oceans already !
hold 38000Gt of dissolved inorganic carbon. CO2 may be !
disposed in empty gas wells as well. The feasibility of these !
techniques depend on the technological advancements we make !
in future and the economics involved. Another option is to use !
CO2 for enhanced oil and gas recovery and this is already being !
practiced widely, especially in view of the increased petroleum !
prices. Some of the CO2 used for oil recovery stays in the ground !
for a long period. Beware that this option will not combat global !
warming.



CO2 disposal (ii)

Saline aquifiers is another option, which has a huge potential. Such
aquifiers are sedimentary rocks (such as sandstone), which are porous
enough to store great volumes of CO2 and at the same time permeable
enough to allow fluid flow. Storage will take place at 7 800 m depths,
where CO2 behaves as a fluid.!
!
Un-mineable coal seams is another place for storage of CO2. In
Enhanced Coal Bed Methane projects (ECBM), coal is allowed to
adsorb CO2 and methane is displaced, enhancing its production.



CO2 disposal (iii)

A scheme for capture, transport and storage of CO2!

It is estimated that CO2 emissions can be reduced by about !
240GtCO2. This means that for Europe alone, it will be !
>30GtCO2. Between now and 2050, this would equate to a !
progressive diminution of 60% in CO2 emissions from power!
generation.



CO2 transport

!



CO2 chemistry!
Besides using for cooling and gasifying drinks, CO2 is also !
used for the production of chemicals and fertilizers, like urea. !
!
Another future option is the hydrogenation of CO2 to methanol and then use !
methanol as a fuel. In this mode, CO2 is repeatedly recycled effectively. However, !
the problem link in this chain is the source of H2. The H2 used in the process!
should not be derived from fossil fuels.!
!
CO2 + 3H2 ! !CH3OH + H2O !H298 = -50kJ/mol!
! !!
These reactions are exothermic with a net decrease in molar volume. !
Methanol formation is therefore favoured by high pressure and low temperature. !
!
The reverse water-gas shift occurs as a side reaction, during such processes.!
!
CO2 + H2 !H2O + CO !H = 41kJ/mol ! !!
!
Since the reverse water-gas shift is endothermic, the conversion of CO2 to CO !
increases as temperature increases.!


Methanol synthesis!
G.C. Chinchen, K. Mansfield and M.S. Spencer,

Chemtech, November 1990



Methanol from CO2!

Existing process:

MeOH is synthesized from syngas (CO2/CO/H2), using typically Cu/ZnO/Al2O3

catalyst at about 250C and 50 bars pressure.

Synthesis of MeOH from CO free feed gas requires modifications to the existing

processes, which are tailored for syngas. Cu on ZrO2 has been suggested as a good

catalyst for CO2 hydrogenation to methanol and more research is needed in this area.

It is possible to raise the ratio of CO2 in the gas feed by adding it to the stream,

by suitably amending the existing process.

It is useful to note that even in the existing syngas based process, the methanol

formation from the CO component is negligible. Therefore, it should be possible

to find a satisfactory process technology for producing MeOH from a relatively

CO lean gas feed.



moderate the setting time. This basic mixture is known as portland cement.
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01%+/ /,2
*%++'$/O(>!$'RO.,$(,O%)!)%QE!9;NK:!
! 34+%
! %/,#
Cement manufacturing accounts for 5% of the worlds

Figure 2-1 Composition of clinker (Odigure, J, 1996)
To reduce the CO2 emission alternative CO2 neutral fuels can be used and often cement is a
CO2 emissions and is one of the most CO2 intensive
mixture of other materials such as clay and ash as well as raw limestone which lower the
products manufactured today with an average CO2

embedded CO2 of the final cement product. The production of clinker liberates CO2 from both
the carbonate material itself and through the fuel combustion process resulting in high CO 2
intensity
Technical Report of 626 kg/t of cement. The main component of
"!
cement known as clinker is the most CO2 intensive
ECRA Project Report about CO reuse from cement production / MeOH and Methane
Synthesis
! 2
component and is produced by applying heat to

carbonate minerals such as limestone (CaCO3)

10/09/2013
M.E. Thesis R. CorcoranRonan

2013,Corcoran
UCD
- 06372805

ME Energy Systems,
Supervisor: Prof. K.R. Thampi
University College Dublin,Energy
Renewable Ireland 2013-14

Re-Use of CO2 ?!!



Oxyfuel cement plant scheme (ECRA, 2011)



Methanol Production Process

Table 4-3 Methanol demand predictions
2022 Predicted Demand (Mt)

IHS Research 137
GBI Research 150.85
Average Prediction 143.9
Viable demand-supply !!!!! ????

The IHS research estimates that 42 Mt RIWKHZRUOGVPHWKDQROGHPDQGZLOOFRPHIURP
M.E. Thesis R. Corcoran 2013, UCD

outside ofProf.K.R.
China (IHS Research,
Thampi, 2013).
Masters According to IHS research, (XURSHV GHPDQG
66
DV D

SHUFHQWDJH RI WKH ZRUOGV
Renewable EnergyH[FOXGLQJ
2013-141RUWK

(astern Asia (China) in 2016 is 30.4% using this
Methanol synthesis plant!
Appropriate modifications are required to this NG based process, when using CO2 feedstock. CO2

may be added to H2 + CO rich gas stream or run only with CO2 + H2 feed.




!"#$%&'()*&+&(,)-&.&'#/0)1/'2&+3)
! !
4.6 Patents !
Renewable methanol production using CO2 rich feeds are currently a reality. The renewable
Figureits
methanol company CRI (Carbon Recycling International) has announced 4-3plans
Massto balance
expand for methanol synthesis. !
production in a joint venture with the methanol production company Methanex (CRI, 2013).
A BAT (Best Available Technology) cement plant producing
!
2,586 tonnes of CO2 per day would
require 362 tonnes of H2 per day. The quantity of methanol produced would be 1,888 tpd. This is
equivalent to a small scale conventional plant but is much greater than the current largest
renewable methanol plant. It is conceivable that a methanol production plant could
accommodate a CO2 rich feed of 2,586 tons of CO2 per day while producing 1,888 tonnes of
methanol. In such a plant to account for the low reactivity CO2 approximately 2-3 times the
amount of catalyst would be required. Increased water formation from the CO2 to methanol
Technical Report
conversion process would increase the energy demand for distillation. The heat produced per
mole of methanol generated from CO2 is lower than that of methanol generated from
ECRA Project CO. This about CO2 reuse from
Report
would reduce the demand on active heat removal from the synthesisSynthesis
reactor compared to a
reactor in a conventional methanol production plant.
Figure 4-4 The "George Olah" plant in Svartsengi Iceland (ThinkGeoEnergy, 2012) Figure 4-5 Electrolysis unit at the "George Olah" plant in Svartsengi Iceland (ThinkGeoEnergy, 2012)
The CRI plant uses CO2 from geothermal sources and hydrogen produced by BAE (Bipolar
CRI uses patented (PLVVLRQV WR OLTXLG WHFKQRORJ\ ZKLFK through a multiple of reactors 10/09/20
Alkaline Electrolysis) using ideally geothermal power. (Singh, Freyr, bjornsson, & Tran, 2012).
combines CO2 and H2 in a reaction loop to produce methanol and water. The reaction is
Prof.K.R. Thampi,7KHMasters Ronan
68
&5, SDWHQWHG SURFHVV KDV DQ HVWLPDWHG WKHUPDO HIILFLHQF\ RI DFFRUGLQJ Corcoran
WR
3DUVRQV
performed at approximately 225 C and a pressure of 5 MPa over a metal catalyst supported on

a metal oxide. Using heat exchangers and a condenser, heat is removed and the methanol is
DQG%ULQFNHUKRII (Parasons Brinckerhoff, 2011)
ME Energy Systems, Universi
the electricity is sourced from nuclear or renewable energy such as wind the current most
appropriate source of low CO2 hydrogen is through alkaline electrolysis. Research is being
conducted into high temperature and pressure alkaline electrolysis which could further improve
conversion efficiency and unit size (Ganley, 2009).
Table 6-1 Commercial hydrogen production technology summary (Holladay, Hu, King, & Wang, 2009)
Technology Feed Stock Efficiency Maturity References

(Sorensen, 2005)
Alkaline
H20 + Electricity 50-70%6 Commercial (Turner, et al., 2008)
electrolyser
(IEA/HIA, 1988)
(Sorensen, 2005)
PEM
H20 + Electricity 55-75%6 Near Term (Turner, et al., 2008)
electrolyser
(H-Tec Systems)
(National Research
Solid Oxide 7
Council and National
H20 + Electricity + Heat 40-60% Medium Term
electrolyser Academy of
Engineering, 2004)
The PEM electrolytic process has higher conversion efficiency (55-75%) though the short term

durability
Supervisor: Prof.ofK.R.
theThampi

membrane makesProf.K.R.
it expensive
Thampi,(Zeng
Masters& Zhang, 2010). SOEC can have
69

Renewable
efficiencies of up to 90% if the thermal input is Energy
ignored2013-14

(National Research Council and National
the high pressure alkaline S-556 unit manufactured by IHT.
Table 6-2 Commercially available electrolysis units (NEL Hydrogen, 2012) (IHT, 2008) (NREL , 2004)
Power H2 Product
System Pressure
H2 Production Required for
Manufacturer Technology Energy
Rate Max H2
Requirements
Production
kWh/kg of H2 kg/yr kW (bar) Gauge

Teledyne Bipolar Alkaline 59.0 67.9 2,200 33,000 17-240 4.1 -7.9
Stuart Bipolar Alkaline 53.4 54.5 2,400 71,000 15-360 24.8
Bipolar Alkaline
53.4 7,900 47,000 48-290 15.9
(High Pressure)
Norsk Hydro
Bipolar Alkaline 39,000
53.4 240-2,300 0.02
(Atmospheric) 380,000
IHT Alkaline 150,000-
47.8 51.1 8
327.4-3,500 1-32
(S-556) (High Pressure) 600,000
NEL Alkaline
Hydrogen (Atmospheric) 45.6 8,664-394,200
9
41-2,175 0.02-0.05
(Nel A)



!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!
known electrolysis plant shown in Figure 6-8. The plant which is located in Zimbabwe uses 28
alkaline electrolysis (S-556) units and has a production capacity of 1890 kg/hr (IHT).
Figure 6-8 Sable Chemical Industries electrolysis plant (IHT)

Renewable
The properties of the IHT alkaline Energyare
electrolysis 2013-14
shown
in Table 6-3. This unit has been
!
Figure 5-5 Methane synthesis mass balance
To convert 1 tonne of CO2 into methane gas consumes 186.7 kg of hydrogen and generates a
considerable amount of heat through the exothermic reaction. A typical cement plant (BAT

plant)
Supervisor: producing
Prof. 3,000 tpd clinker and generating 2,586 tonnes of CO2 per day would require
K.R. Thampi

482.8 tonnes of hydrogen and would produce
Prof.K.R. 940 tonnes
Thampi, Mastersof methane gas per day. 72


between 47.8 51.1 kWh and has a guaranteed maximum energy consumption of 51.7 kWh
per kg of hydrogen. Figure 6-9 below shows a mass balance and energy balance to produce 1
tonne of hydrogen based on maximum production rate and the guaranteed maximum energy
consumption of an S-556 electrolysis unit.
Figure
M.E. Thesis 6-9 Mass2013,
R. Corcoran balance for hydrogen production using and S-556 alkaline electrolysis unit
UCD


At an assumed price of 8 cents per kWh the production of 1 tonne of hydrogen amounts

to 4136
euro. Water electrolysis produces 8 Renewable
tonnes of Energy 2013-14
oxygen
every tonne of hydrogen produced.
for
differences in the price of gas. Because of the higher prices in non US gas markets, energy
companies have begun the construction of LNG (liquefied natural gas) plants with the goal of
compressing natural gas for ship transportation to markets where the prices are higher (BG
Group) (Reuters, 2013).
Table 5-3 Natural Gas prices by location (BP, 2013)
Unit US dollars per million Btu Euro per MWh

Germany (Average Import Price) 11.03 28.2
UK (Heren NBP Index) 9.46 24.2
US (Henry Hub) 2.76 7.10
Alberta 2.27 5.80
Shown in Table 5-3 are the prices of natural gas in different locations. It can be seen that the
price of natural gas in Germany is near 4 times the price in the US or Alberta. Currently this is
advantageous for the prospect of generating synthetic methane in Germany, though transport of
natural gas between markets in the form of LNG may reduce the price disparities.


Prof.K.R. Thampi,
"#! Masters 74

! Renewable Energy 2013-14

Table 7-4 Methanol: Daily financial balance
!
Daily Financial Balance
7.1 Case Study: 35% of CO2 emissions for methanol synthesis
! Costs 523,215 GD\
Incomes 256,667 GD\
The waste heat generated from the exothermic synthesis of 630 tonnes of methanol is 975 G
Losses 266,548 GD\
Using an ORC this waste heat can be converted to electrical energy providing 159 MWh
electricity. At a price of 80 euro per MWh, the electrical energy generated is worth 12,720 euro
!
Table 7-4 contains the financial figures form the case s
shows that generating methanol in this way is very costly a
7.2 Economic evaluation
the high electrical energy consumption of electrolysis. H
Table 7-2 Methanol: Primary costs.
unable to compete with hydrogen sourced from fossil fuels
Quantity Specific cost Cost
CO2 captured 866.25 tonne WRQQH GD\
"#!
Hydrogen Generated 118.125 tonne WRQQH
! GD\
Primary costs arise from the electrolytic production of hydrogen and the cost of carbon capture.
The costs here are capture costs and are not inclusive of purification or transportation.
Table 7-3 Methanol: Primary income

Figure 7-2 Mass balance flow for methanol synthesis. Figure 7-3 Renewable electricity to methanol (Energy conversion efficiency)
Quantity The energy conversion

Specific efficiency from renewable
Cost Incomeenergy to methanol is shown in Figure 7
The mass balance flow diagram for methanol synthesis is shown in Figure 7-2. At a 35% CO2
Renewable electricity is drawn from the grid and thus is assumed 100% of the starting pow
capture rate for methanol synthesis 866 tonnesGeneration
Methanol 630
of CO2 is captured and 118 tonne
tonnes of hydrogen WRQQH 234,GD\
The hydrogen production process using an IHT S-556 electrolyser is 64% efficient. T
is required to produce 630 tonnes CO
of methanol.
credit cost
2 electrolytic process converts 64% of the electrical energy into hydrogen. The metha
866 tonne WRQQH GD\
synthesis reaction converts 66.6 % of the starting hydrogen into methanol and the other 33.3
The electrolysis plant would needavoided
a production capacity of 118 tonnes per day. The current
is converted to water.
largest electrolysis plant is SableExcess
ChemicalOxygen
Industries and has a production capacity of 45.4
105 tonne WRQQH GD\
tonnes per day. Producing 118 tonnes of hydrogen per day requires a plant 2.6 times the
size
waste heat power
and capacity of WKHFXUUHQWZRUOGVODUJHVW electrolysis plant. 159 MWh 0:K GD\
production Prof.K.R. Thampi, Masters 75

M.E. Thesis
Some R. Corcoran
of the oxygen 2013,
by-product UCD

from electrolysis can be used to provide oxygen for an The overall energy conversion efficiency of electrical energy to methanol is shown to be 42.67
oxyfuel


(7-1).
cement plant. Using 840 tonnes with the oxyfuelled kiln the excess oxygen would amount to 105
!
CO2 credit cost
866 tonnes
avoided
Excess Oxygen 420 tonnes
waste heat power
320 MWh
production
!
Methane gas imports for Germany had an average price

7.4 Economic evaluation
a price of 442 euro per tonne. The excess oxygen coul
Table 7-5 Methane: Primary Costs
tonne. Methanation generates a larger quantity of h
Quantity Specific Cost methanol synthesis does and therefore provides more
Cost
CO2 captured 866.25 tonne WRQQH generated. Using this waste heat 320 MWh can be ge
GD\
Hydrogen euro worth of electricity.
157.5 tonne WRQQH GD\
Generated
Table 7-7 Methane: Daily financial balance
Figure 7-5 Renewable electricity to methane (Energy conversion efficiency)
Daily Financial Balance
The energy conversion efficiency from renewable energy to methane is shown in Figure 7
Generating 157.5 tonnes of hydrogen for the methanation of 866 tonnes of CO2 costs 651,420
Renewable electricity is drawn 686,070
Costsfrom the grid and thus is assumed GD\
to be the starting energy
euro and is the single largest cost.
production process using an IHT 190,196
is 100%. The hydrogen incomes GD\ is 64% efficie
S-556 electrolyser
Figure 7-4 Mass balance flow for methane synthesis The electrolytic process Losses
converts 64% of the electrical energy into GD\
495,874 hydrogen. The metha
Table 7-6 Methane: Primary Income
synthesis reaction converts 50 % of the starting hydrogen into methane and the other 50%
ethanation of 866 tonnes of CO2 requires 158 tonnes of hydrogen to produce 315 tonnes
converted to water. Income
Quantity Specific Cost
hane gas. Converting CO2 to methane gas requires a third more hydrogen than "#!
Methane !
ing CO2 to methanol. The increase 315in hydrogen
tonnesdemand perWRQQH
mole of CO2 requires aGD\
Generation
OHFWURO\VLVSODQWWKDWLVWLPHVWKHVL]HRI6DEOH&KHPLFDO,QGXVWU\VSODQWLQ=LPEDEZH
CO2 credit cost
866 tonnes WRQQH The overall energyGD\
conversion efficiency of electrical energy to methane is shown to be 32
mand foravoided
158 tonnes of electrolytically produced hydrogen generates 1,260 (7-1).of oxygen.
840 tonnes per day
Excess in an oxyfuel cement
Oxygen 420 kilntonnes
leaves a large excess of 420 tonnes of CO2 GD\
WRQQH

y to be sold.
waste heat power Supervisor: Prof. K.R. Thampi

320 MWh 0:K GD\
production Prof.K.R. Thampi, Masters 76

aste heat from the exothermic formation of 215 tonnes of methane is relatively large at

GJ of energy. Using an ORC to convert this heat to electricity provides 320 MWh of
More CO2 chemistry!
CO2 + H2 !H2O + CO !H = 41kJ/mol ! !!
!
Since the reverse water-gas shift is endothermic, the conversion of CO2 to CO !
increases as temperature increases.!
Another relevant reaction in this series is the Boudouard reaction:!
2CO ! !CO2 + C, which affects the stability of the catalyst and the
operation of the reactor. !
The deposited carbon can foul the plant operation, when the rate of Boudouard !
reaction picks up.!
!
The Sabatier reactions also play important roles in CO2 chemistry (depending !
on the reaction conditions and the type of catalyst):!
!
CO2 + 4H2 ! !CH4 + 2H2O !
CO + 3H2 ! !CH4 + H2O!
!
These reactions are used to clean up traces of CO from H2 produced from liquid
and gaseous feedstocks for fuel cell operation.



CH4 + CO2 Reforming

CO2 + CH4

2CO + 2H2
H298K = +261.0kJ/mol

We will study this important reaction in more detail in this course, later. This reaction

is relevant to high temperature fuel cells, particularly SOFC (solid oxide fuel cells).

Thermodynamic data:

Ref. J.R. Rostrup-Nielsen, J. Catal., 27, 343, 1972.



Criteria for evaluating energy supply systems

Source: C.J. Winter, H2 as an energy carrier



Dual use of renewable energy
sources

Sometimes, a renewable energy source may have more than one potential use.

A good example is NG (natural gas, CH4 primarily), which is a fuel as well as

an excellent chemical feedstock. Another example, is hydrogen.

Here we will glance through the uses of CH4. The course will look at hydrogen energy

in detail, later.

Some of the chemical reactions, which made the present fossil fuel and feedstock based

technology successful, are equally relevant and useful for developing future

technologies based on renewable energy and green chemistry.

C1 chemistry becomes very relevant here, both for the use of bio-NG as a feedstock

and recycling of CO2.



NG as a chemical building block

K.R. Thampi in Recent developments in catalysis

B. Viswanathan and C.N. Pillai,( eds)


Narosa Publishers, 1990.


C1 Reactions relevant to both the fossil fuel based and the future
renewable technologies

K.R. Thampi in Recent developments in catalysis

B. Viswanathan and C.N. Pillai,( eds)

Narosa Publishers, 1990.



Energy and pollution from transportation

Transportation sector is by far the largest polluting segment. It also consumes

a significant share of our energy pie. By addressing this sector, we can make a

significant positive impact on the energy consumption and resulting global

pollution.

The required energy conversion stations can be centralized, mid-sized, local or

even a part of the vehicle itself.

The source could be NG, solar, biomass derived products, hydrocarbons, hydrogen,

etc. Conversion methods could be solar cells, fuel cells and electrolysers.

Energy storage devices are also required in most cases.

The use of hydrogen as a fuel is often heard for transportation applications. But, it

is facing a lot of criticism and there are many unanswered questions.



Fuel choice for transportation



Various synthetic fuels for transportation



Bio-fuels for
automobiles



Sugar to alcohol

Alcohol is usually produced from sugars (starch including) by biochemical

methods. Yeast and enzyme reactors are generally used. There is a possibility

for using lignin as well for alcohol production. But, this is still in research stage.

Unfortunately, some of these processes used to produce alcohols lead to ground

water pollution, due to the discharge of large amounts of water having high

BOD (biological oxygen demand) and COD (chemical oxygen demand) values.

This is not acceptable.



Ethanol as a fuel or as an energy store

Advantages

- Ethanol may be produced from sugars, cereals and other

photosynthetic natural products

- Bio-ethanol can be stored and transported

- Bio-ethanol then could be used for running engines as a liquid fuel

- Bio-ethanol may be used as a building block in chemical syntheses

- It can be steam-reformed to produce hydrogen

- It can be used as a fuel to run fuel cells (directly or via hydrogen)

- Required technology is already in place

- Bio-ethanol is CO2 neutral

- Energy density value is good (120.7 kJ/g)

- can be sized to large, medium and small sized production units

- creates local employment in farming communities and villages



Disadvantages of ethanol

-The net gain in energy gained is small

-Production of ethanol itself causes some environmental issues (waste water)

-Use of ethanol in engines may lead to the emission of side products (air pollution)

-Bio-ethanol has to be produced without affecting the food security and availability

* Pollution related issues can be addressed by suitable adaptation of technology



A summary on CO2 recycling

In brief, both CO2 and H2 may be stored together in the form !
of alcohols. This is considered as a storage of chemical energy, !
which will serve as a convenient fuel and chemical feedstock !
for many applications. Such a transportable fuel can serve both !
chemical and transportation industries and also reduce global !
CO2 emissions. !
!
When the required CO2 for the reaction is concentrated and !
obtained from atmosphere or polluting sources, and the required!
H2 is derived from non-fossil fuel resources, we can satisfy the!
basic requirements of calling it a green fuel or sustainable energy!
feedstock. The required energy input for running the reaction!
process should also be non-polluting.



Be aware that farmers already feed in increased levels of CO2 gas into their

greenhouses to increase the yield of crops.



Towards Zero Emissions from fossil fuels!
There are three options on this!

!
1) Post combustion capture by chemical means and !
!then dispose off!
!
2) Pre-combustion capture (through syngas and !
!shift reactions); CO2 will be separated and disposed
off!
!
3) Oxy-fuel firing: use of O2 instead of air for burning, !
!which produces only water and CO2. Water will be !
!condensed and CO2 stored.!



Industrial CO2 capture and process treatment!


A functioning plant"
for CO2 handling and
treatment!


CO2 injection



Fuel choice, examples

Today we shall look at two options available as fuel choice, where both are derived

photosynthetically and hence are CO2 neutral:

1) Bio-ethanol
: may be used as a fuel directly, or as

2) H2

: through steam reforming

We shall also briefly look at the level of our technical maturity in adapting our

needs to these alternate fuels produced in a CO2 neutral manner.



H2 production processes to remember

-Thermochemical

- steam reforming

- gasification*

- pyrolysis*

-Electrochemical

-Photobiological

-Photoelectrochemical

-* only for solid biomass



The current technology for producing H2 is too costly and energy intensive.

The source should be CO2 neutral, too. In nature, H2 is always present in

bound form in organic compounds and water. H2 can be produced from fossil

fuels (as it is done today, mostly), biomass, NG, bio-NG, alcohols or water.

For the near future, technologies for efficiently producing H2 from renewable sources should

be developed and deployed. Though the basic science is available, technological problems

compounded with economic issues prevent such processes becoming viable in our daily life.



Processes



Thermochemical

Steam reforming of EtOH

C2H
5OH + 3H2O

2CO2 + 6H2
(H298 =+347.4kJ/mol)

is a multi-step reaction involving also several unwanted side steps:

C2H5OH + H2O

CH4 + CO2 + 2H2

C2H5OH

CH4 + CO + H2

C2H5OH + H2O

2CO + 4H2

CH4 + H2O

CO + 3H2

CO + H2O

CO2 + H2

Note the syngas and WG-shift reactions. In addition, methanation, Boudourd,

dehydrogenation, decarbonylation and acetic acid formation may also occur.

ZnO and many metal loaded catalysts are good for the required reaction.



cement production significant area will be required for the production of algal biomass.
Figure 8-1 Ecoduna: Thin film closed algae production system (ECODUNA, 2011)
The biomass production rate per area is an important factor as directly affects the area
requirements for sequestering CO2 in biomass. There are broadly three types of algae
http://eu.is.not.only.brussels.nweurope.eu/

cultivation systems that produce biomass at different rates and with different efficiencies of CO 2
Look at this web uptake.
documentary (5:56 min)
The production rate for each system are as follows, open systems (10-20 g/m d), closed 2
located in projectsystems
ALGAE (35-49and
g/m then
d) and follow
2 2
modern thin film closed systems (80-100 g/m d) (see Figure 8-1).
video in tab 2.

"#!
!


See also these projects web sites

Highlights: 1) My work in En Algae is one of the 5 themes selected by the EU to

be highlighted as a success story in this documentary film by the EU:
http://eu.is.not.only.brussels.nweurope.eu/

2) Arbor is selected as a RegioStars 2014 awards Finalist under the
Sustainable growth: Green growth and jobs through Bio-economy (Final is
in March 2014)

3) I am a finalist in the Sustainable Energy of Ireland Awards 2013 Research
Category: Work on Oxygen tolerant solar cells, Patented



End of Part I

In brief, we have seen by now what is the meaning of sustainable and renewable energy.

We have also seen why it is so important to go for CO2 neutral fuels.

The topic of global warming is considered.

The role of CO2 and CH4 on the greenhouse gas effect has been discussed.

The chemical mechanism of greenhouse gas effect: to be studied as an exercise.

We studied the ways and means of mitigating and recycling CO2.

Chemical storage of energy has been considered, with alcohols as an example.

The role of CO2 in methanol synthesis has been highlighted in the context of capturing

and re-using CO2 from power plants. We have also seen CO2 reforming of methane.

Among CO2 neutral bio-fuels, ethanol was considered as an example. Its role as

an energy storage medium and its utility in hydrogen economy has been looked at.

C1 reactions, fundamental to hydrocarbon chemistry and renewable energy options

have been listed out. Tables on energy units, fuel choice, energy density, etc. have been

provided. Existing processes related to syngas and H2 production needs to be studied for

making it equally relevant for CO2 neutral fuel processes for the future.



Chemical Processes of Sustainable and Renewable Energy

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Chemical Processes of sustainable and renewable energy

General Contents & Course Structure

1. Aims of this course

Prof.K.R. Thampi, Masters 1

Sustainability means having the ability to meet the needs of a

Prof.K.R. Thampi, Masters 2

-Thermodynamic principles of energy conversion

Prof.K.R. Thampi, Masters 4

Prof.K.R. Thampi, Masters 6

1970 1990 2010 2030 *mainly non-sustainable

Biodiesel (FT) T&D blend Hydrogen Hybrid

Bio-Syngas T&D blend

WEC/PSI (2011): Global Transport Scenarios 2050

2% demand growth demand exceeds supply

1900 1950 2000 2050 2100

World Oil Reserves/Consumption

Prof.K.R. Thampi, Masters 13

Limits on consumption by the affluent societies, better fuel

Even in developing countries, economic growth has been

The demand for oil as opposed to the supply will reach

+,-,./01,2 Europe Direct is a service to help you find answers

Prof.K.R. Thampi, Masters 19

Prof.K.R. Thampi, Masters 20

J. Jensen, Energy Storage (1980)

Prof.K.R. Thampi, Masters 21

2.3901104kcal (thermochemical, food, etc.)

Prof.K.R. Thampi, Masters 23

watt (SI unit) W = 1W = 1J/s = 1Nm/s = 1kgm2/s3

Prof.K.R. Thampi, Masters 24

1 J 238.9 x 10-6 278 x 10-6

1kWh 3.6 x 106 860

1 MWy 31.54 x 1012 7.53 x 109 8760 x 103

1 ton pit coal contains 29.3 x 109 7 x 106 8150

1 m3 NG contains 35.2 x 106 8400 9.8

1 ton crude oil contains 41.9 x 109 107 11650

1 kg 235U contains 82 x 1012 19.6 x 109 22.8 x 106

Prof.K.R. Thampi, Masters 25

Prof.K.R. Thampi, Masters 27

from Arthur Nozik Prof.K.R. Thampi, Masters 28

Prof.K.R. Thampi, Masters 29

Prof.K.R. Thampi, Masters 30

J. Jensen, Energy Storage (1980)

Prof.K.R. Thampi, Masters 31

Prof.K.R. Thampi, Masters 36

CO2 as a case study

Energy and chemical building blocks

Gas, liquid and solid energy vectors

Criteria for renewable options in energy

Prof.K.R. Thampi, Masters 37

In spite of all efforts to curb emissions of polluting gases like

Prof.K.R. Thampi, Masters 38

6 Gtc : burning fossil fuels

But the regular addition of > 8Gtc/year upsets the delicate

Prof.K.R. Thampi, Masters 39

Prof.K.R. Thampi, Masters 40

Prof.K.R. Thampi, Masters 41

Comparison of measured sea surface temperatures in the Western Pacific

Proceedings of the National Academy of Sciences, DOI:10.1073/pnas.0606291103; J.E. Hansen et al.

Prof.K.R. Thampi, Masters 42

Global warming comes from the shift of the heat transfer

Prof.K.R. Thampi, Masters 44

Total blackbody radiation

Temperature of planet adjusts to level where blackbody radiation