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Unit IV: Bio-Energy, Geothermal: G. Suriya Narayanan, TF, Dee, Nitt
Unit IV: Bio-Energy, Geothermal: G. Suriya Narayanan, TF, Dee, Nitt
Unit IV: Bio-Energy, Geothermal: G. Suriya Narayanan, TF, Dee, Nitt
G. Suriya narayanan,
TF, DEE, NITT
06/19/2020 Unit IV 1
Definitions
Biomass
A renewable energy source and a material of biological origin, which derived form organic
matters of recently living biological materials and animal wastes.
*Different forms of bio-energy are bio-power, heat, solid, liquid and gas.
Biomass is a form of renewable energy source, because the energy contained in the
biomass is energy from the sun captured through natural process of photosynthesis and
renewable CO2 and H2O.
If the biomass is a renewable energy source, then bio-energy form of renewable energy.
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• Bio energy
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• Bio energy
C, O2, H, N, S + ‘inorg’ – bio molecules (carb, prot & fat) and H2O.
• Constituents of plant
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Cellulose : Linear, un-branched, fibrous, tough, water in-
soluble polymer (homo polysaccharide, DOP-10k to 15k
units of D-glucose) – cell wall – 41-55%.
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Lignin: Rigid polymer - complex str - ‘phenyl alanine &
tyrosine; glucose’ – 2nd to cellulose – covalent crosslink to
cellulose, which complicates ‘cellulase’ degradation - 30%
of mass of wood.
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Hemicellulose: soluble ‘alkali & acid’ soln – yields simple sugars e.g.
more than one ‘monosac’ – DOP is b/w 100 to 200 – ‘polyuronides &
cellulosans’.
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Bio-energy ‘Feedstock’ biomass derived materials energy containing
products - Thru’ - heat, chemical treatment, microbial activity.
The feedstock – (i) forest (lingo-cellulosic or woody), (ii) agriculture
(woody/non-woody), (iii) waste sources, (iv) microalgae – emerging imp.
feedstock source of bioenergy.
The biomaterials of interest – sugar/starch, cellulose/lignocellulose or
lipids/oils.
1st gen: ‘oils & sugars’ – food crops. e.g. bio-ethanol from corn, bio-diesel
from soybean
2nd gen: ‘non-food’ crops. E.g. perennial grasses, woody material, forest
harvests and non-food portion (left-over) of food crops.
3rd gen: algae – higher yields
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Forest based ‘feedstock’
•Provides → woody (lingo-cellulosic/cellulosic) in nature → source of fuel for cooking and
space heating.
•‘Extended-rotation’ forests – e.g. pine trees (Pinus resinosa, (red pine or Norway pine),
Pinus strobus (white pine), managed specially to provide ‘biomass’.
•Woody material available – barks (high energy density, K and Si), wood chips (used
directly as solid form of biofuel for combustion, or densified / pelletized).
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Agricultural based ‘feedstock’
• 1st generation biofuel feedstock
• Regarded as sources of sugars, starches, lipids, woody biomasses – the
feedstock – crops grown for ‘energy production’ (i.e dedicated bio-energy
crops), agricultural residues (non-edible, cellulosic materials remains after
harvesting of ‘edible’ portion.
• Dedicated ‘bio-energy’ crops – ‘annual crops e.g. corn’ – grown for their sugar,
starch or oil content, and ‘perennial herbaceous non-food’ plants, which grown
for ‘cellulose’.
• Bio-ethanol e.g. sugar cane (Saccharum officinarum, prime feedstock in
brazil), corn (Zea mays, in USA), Sugar beets (Beta vulgaris), potatoes
(Solanum tuberosum), sorghum (Sorghum bicolor) and cassava (Manihot
esculenta).
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Agricultural based ‘feedstock’
▪ About 60% of bio-ethanol prodn → Sugar cane & Corn (Brazil and USA).
▪ Bio-diesel production → crops contain high amt of lipid content – e.g. soybean (Glycine
max), Oil palm (Arecaceae), Rapeseed (Brassica napus).
▪ Soybean – primary feedstock for ‘bio-diesel’ production in USA, Brazil, Argentina,
European countries (World leaders in ‘bio-diesel’ production’)
▪Perennial crops (e.g. hybrid poplars, willows) → not a food crop → sources of
‘lignocellulosic’ biomass for 2nd gen biofuel → ‘long term yield potential’ not seasonal,
grown more than one season, don’t have to be planted → environmental benefits → soil
corrosion prevention, water quality improvement and wildlife habitat.
▪Perennial crops also includes herbaceous perennial plants (lacks woody ‘stem’) and
perennial ‘woody’ stem (e.g. Switch grass, Miscanthus)
▪Potential non-edible oil crops → Castor and Camelina (under ‘R&D’)
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Agricultural based ‘feedstock’ – ‘Perennial crops’
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Waste based bio-energy ‘feedstock’
‘organic matters’ → leftover or remains from industrial, agricultural, agro-
industrial processes or activity, municipal solid waste and animal waste
→ potential feedstock → degradation & energy production.
▪ Industrial wastes → effluents from paper and cellulose mill (humid
sludge), distillery (Anaerobically digested Distillery Spent Wash),
textiles (org. dyes), tanneries, poultry and dairy, and materials from
wood processing industries like sawmill (sawdust, wood shavings).
▪ Agricultural waste → by-products e.g. bagasse (a fibrous material
from sugarcane which is used directly as solid fuel and/or feedstock for
bio-ethanol production), Corn stovers, Rice husk and Wheat straw.
▪ Animal wastes → effluent from Slaughter house industries, farm house
wastes (cow dung) → ‘anaerobic’ → biogas → heat & bioelectricity.
▪ Municipal solid waste → kitchen waste, clothes, other wastes of ‘org
mat’ origin → incinerated → ‘anaerobically fermented’ → biogas.
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Algal biomass as bio-energy feedstock
Challenges meeting the demands for bio-energy feedstocks
includes competition for food, land, water and other resources
(nutrients) ‘plant based biomass feedstock’.
‘Algae’ photosynthetic microbe e.g. ‘Chlorophyte’
provides attractive option doesn’t compete with ‘land, food,
water resources.
Yield is ‘100 fold’ high energy density (15 to 30 MJ Kg-1)
desirable biofuel characteristics (fatty acids formulation) by ‘genetic
alteration or stress’.
All season Ensures continuous supply long term
sustainability is viable added applications like wastewater
treatment, CO2 capture.
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Biomass conversion technologies
Biomass Cooking, heating, steam generation, power generation, by-products.
Conversion methodologies
Thermo-chemical
(i) Combustion
(ii) Pyrolysis
(iii) Gasification
(iv) liquefaction
Chemical conversion
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Biomass conversion technologies
Nature of Lipids – Fatty acids, TAG (triacylglycerol)
pigments, hormones.
at above the same oxidation state as the hydrocarbons in fossil fuel. The
cellular oxidation of ‘FA’ (CO2 + H2O) is ‘exergonic’ like in the ‘IC’ engines.
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Biomass conversion technologies - Lipids
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Biomass conversion technologies - Lipids
Two conventions for naming fatty acids – (a) SFA, (b) PUFA
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Biomass conversion technologies - Lipids
Naturally occurring FA
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Biomass conversion technologies - Lipids
TAG – simplest lipid constructed from ‘FA’ (triglycerides, fats, or neutral fats)
C18:1→ triolein.
Specific gravity
Esterification: 2 routes
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Biomass conversion technologies
Thermo-chemical method
Combustion
The most direct process - req initial high temp (>550°C) – sufficient air
supply (O2) and not too high moisture – BM to residual ash – appln cooking,
heating and co-gen. essentials are BM, O2 and ignition source.
Type of Combustor used: (i) Fixed bed or grate fired combustors, (ii)
Suspension burners, (iii) fluidized bed system, (iv) Biomass stoves.
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Biomass conversion technologies
Thermo-chemical method
Pyrolysis
Thermal decomposition of org.matter (in BM) in atm of inert – pyrolysis.
The pdt is charcoal, pyroligneous liquid, and some gaseous pdts.
The proportion of these products vary based on (i) operation condtn, (ii) type of
bm used.
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Biomass conversion technologies
Bio-chemical method
‘BM’ & org.wastes are imp source of ‘elements’, that can be converted into useful pdts by
adopting suitable ‘bio-process’.
Waste material includes animal residues such as cattle dung, poultry litter, MSW (incl. food,
kitchen & market waste), industrial org waste (such as those from food processing industries,
sugar processing, distilleries, pulp & paper), agricultural waste (stover, husk, bagasse).
A bio-chemical conversion process of ‘BM’ & org. waste into ‘biofuel’, is comprises of
(i) hydrolysis of complex bio-materials like carb, proteins, fats, into simple monomers of C & N
sources,
(ii) the synthesis of complex molecules from the simple substances. The process is accompanied
by the release of energy used for the cell growth and maintenance and useful pdt.
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Biomass conversion technologies
Anaerobic digestion of ‘BM’ and Org. waste to produce Bio-gas
‘AD’ is multistep ‘biological’ and chemical process waste removal and Energy
production. 4 steps
(i) hydrolysis,
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Biomass conversion technologies
Anaerobic digestion of ‘BM’ and Org. waste to produce Bio-gas
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Biomass conversion technologies
Anaerobic digestion of ‘BM’ and Org. waste to produce Bio-gas
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Chemistry and Biochemistry of biomass
Biomass pre-treatment methods – Fractionation of Cellulose/Hemi/Lignin
Chemical Pre-treatment
Acid based
Alkali based
Ozonolysis
Ultrasonic methods
Organic solvents
Ionic liquids
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Chemistry and Biochemistry of biomass
Biomass pre-treatment – Chemical – Acid
Acid hydrolysis of ‘hemicellulose and lignin’ cellulose.
Most widely used ‘H2SO4’ – others were HCl, H3PO3, HNO3, C2H4O3,
C2H2O4, HCOOH and CH3COOH.
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Chemistry and Biochemistry of biomass
Biomass pre-treatment – Chemical – Acid
e.g. Corn pretreatment by oxalic acid 13% yield with low level inhibitors – yield is 10%
when maleic acid.
‘Rice husk’ pretreatment – aq.NH3 (96%) & H2SO4 (90%) – combined better removal of
‘lignin & hemi’.
Eulaliopsis binate (a perennial plant) with H2SO4 @opt condtn – 21% tot. sug+ 3.2%
lignin+3.3% acetic acid with low inh.
‘Corn stover’ pretreated with ‘steam+dil. H2SO4’ 78% yield.
Acid treatment is cheap – but req high temp – high energy input – costly – corrosive –
req spl reactor vessel – must be resistant – acid treatment generates inhibitors that must
be removed.
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Chemistry and Biochemistry of biomass
Biomass pre-treatment – Chemical – Alkali
‘BM’ treated hydroxides of Na, K, Ca, NH3 @ normal temp & p.
eff removal for lignin than acid high acc of enz., towards ‘hemi’ becoz.,
removal of ‘acetyl & uronic’ acid grp on hemi.
Ester linkage b/w xylan & hemi is hydrolyzed.
NaOH – more eff – Ca(OH)2 – widely used alkali which also removes ester link
b/w lignin & carbs, and acetyl grp, which enh ‘cellulose’ digestibility.
Wheat straw, Poplar wood, switchgrass, corn stover.
Add benef: low reagent cost & less safety req, but need huge amt of water for
washing salts of alkali.
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Chemistry and Biochemistry of biomass
Biomass pre-treatment – Ozone
‘Ozonolysis: O3 powerful Ox. Agent reacts preferably reacts with
‘lignin’ than ‘carbs’, and deg ‘lignin’ by attacking the ‘aromatic’ ring.
Used to disrupt str of ‘LC’ materials such as ‘bagasse, pine, peanut, cotton
& wheat straw’.
Performed @ mild operating conditions (room t & p), and doesn’t produce
toxic residues. Short-chain carboxylic acids are the main inhibitory
compounds generated properly removed by water washing.
furfural and HMF (5-hydroxymethylfurfural), are not found in ozone-
pretreated hydrolysates.
Process factors: moisture, particle size, reactor design, pH, conc., flow, and
time.
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Chemistry and Biochemistry of biomass
Biomass pre-treatment – Ozone-Advantages
Low generation of inhibitory compounds, and specially the no generation of furfural and HMF (which
might hinder following downstream stages).
On-site ozone generation and direct utilization (avoiding problems related to chemical supply and
storage).
Reduction of environmental pollution with a suitable process design, decomposing residual ozone at the
end of the process.
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Chemistry and Biochemistry of biomass
Biomass pre-treatment – Ozone
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Chemistry and Biochemistry of biomass
Biomass pre-treatment – Ozone- Dis-advantages
Highly reactive, flammable, corrosive and toxic characteristics of ozone,
leading to potentially dangerous processes
Exothermic characteristics of process may require cooling systems
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Chemistry and Biochemistry of biomass
Biological pre-treatment (for lignocellulosic BM)
Enzymatic pre-treatment – Degradation of lignocellulose by fungi and bacteria –
degradation of lignin – the role of peroxidases – degradation of cellulose –
Trichoderma cellulases
Enzymes
Enzymatic pre-treatment
Properties imp in terms of microbial or enzymatic attack
Conclusions.
Fungal degradation of lignocelluloses- white, brown and soft rot fungi
Fungal degradation of wood polysaccharide.
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Chemistry and Biochemistry of biomass
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Chemistry and Biochemistry of biomass
Biological pre-treatment - Introduction
Annual production 200b tonne. Uncertainty in basic structure conformation, determine molecular weight,
polydispersity, amorphous, new bonding pattern.
Important Prop in terms of microbial or enzymatic attack:
Lignin polymers have compact structures that are insoluble in water.
The inter-monomeric linkages that account for the rigidity of lignin comprise many kinds of C–C and C–O
bonds with the β-aryl ether linkage being the most significant.
Inter-monomeric linkages in lignin are not hydrolysable.
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Chemistry and Biochemistry of biomass
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Chemistry and Biochemistry of biomass
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Chemistry and Biochemistry of biomass
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Chemistry and Biochemistry of biomass
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Chemistry and Biochemistry of biomass
Pleurotus ostreatus
Phellinus weirii
Trametes_versico
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Chemistry and Biochemistry of biomass
Biological pre-treatment – Brown Rot fungi
Also basidiomycetes (7%) yield brown, shrunken cubical cracks easily integrated.
Mostly Gymnosperm – BM recycler.
Evolved from WRF by ‘selective loss’. Strength loss weight loss.
Decrease avg. chain length of Wood polysac (abt 4-fold @ only 10%)
Mechanism of action: during rotting, fungal uses low.mol.wt sp (free radicals) that penetrates the
lignin carbonyl and carboxylic acid grp (oxidative component) hemi is deg more rapidly
cellulose is removed (depolymerization) leaving complex, aromatic ring containing polymer
derived from the original lignin oxidized, (i) demethylation of aromatic rings (increases –OH),
(ii) intro of carboxyl and carbonyl grps.
Lignin still polymeric, and intact 2 concl (i) little cap to deg, (ii) the low molwt sp they use are
oxidants (●OH-centered free radicals, Prime candidates).
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Chemistry and Biochemistry of biomass
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Chemistry and Biochemistry of biomass
Amylocystis lapponica
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Chemistry and Biochemistry of biomass
Gloeophyllum sepiarium
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Chemistry and Biochemistry of biomass
Postia tephroleuca
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Chemistry and Biochemistry of biomass
Postia placenta
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Chemistry and Biochemistry of biomass
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Chemistry and Biochemistry of biomass
Daldinia concentrica
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Chemistry and Biochemistry of biomass
Hypoxylan sp.,
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Chemistry and Biochemistry of biomass
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Chemistry and Biochemistry of biomass
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Feedstock pre-processing and treatment methods
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Geothermal energy, OTECs and Tidal energy
Heat – radiated – earth’s surface space. Solar energy, absorbed by the earth’s soil, rock,
ocean re-emitted as ‘infrared’ radiation, in which 1% of the radiation comes from
earth’s interior.
The energy (in the form of heat), that is present at a few thousand of feet below the earth’s
surface, is more than enough to satisfy the energy needs of every nation of the world
many times. The ‘heat’ energy ‘Geothermal’ energy.
The heat energy is available from (i) the planet’s past history (during the big bang 4.6x10 9
yrs ago) i.e. the hot inner and outer core (ii) radioactive decay of naturally occuring
radioactive isotopes of Th232, K238 and U40.
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Geothermal energy, OTECs and Tidal energy
So, this energy is perpetual (continuing forever), inexhaustible and renewable form (when
compared with the non – renewable energy sources on the basis of ‘resource
depletion’) of energy.
The average heat flux of the geothermal energy over the earth’s surface is 87mW/m2 (global
surface area of earth is 5.1x108 km2 4.4x1013 W of renewable energy potential).
For comparison, the estimated ‘total power consumption’ by all human activity in 2006 was
~1.57x1013 W (2.8 times). This data clearly says that, the heat in the earth has the
potential to significantly contribute to the ‘energy needs’.
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Geothermal energy, OTECs and Tidal energy
The interior of earth : Crust (6-90km) Mantle Outer core Inner core. Only the tiny
fraction of the heat can be extracted from earth’s crust, and the ‘maximum exploitation
depth’ is 5km. To this depth the temp of the crust increases @ an avg rate of 30 to 35°C per
km (mean geothermal gradient).
Becoz of the thermal gradient, natural heat rises (heat flow) by conduction (and by convection in
some places).
The conductive component of ‘heat flow’ also varies varying ‘heat flux’ from min of 30mW/m2
to 500mW/m2, and the avg. heat flux is ‘few thousand times’ less than the ‘mean solar
radiation’ striking the earth’s surface.
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Geothermal energy, OTECs and Tidal energy
The viability of ‘geothermal energy’ conversion is apparent only in places where its heat
dissipates into earth’s surface through a ‘carrier fluid’ such as ‘warm water’ that flows
from ‘geyser’, or through the release of ‘hot gases’, or ‘volcanic eruption’.
Accessible resource base – The amount of heat energy that could be theoretically be
taped (or utilized) within the ‘maximum exploitation depth’ is 14x1025 J, however
only a fraction of it could be used.
At the boundaries b/w the ‘tectonic plates’(where, the molten rock – magma@1000°C,
reaches the surface), the heat flux are high as 300mW/m2.
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Geothermal energy, OTECs and Tidal energy
High heat flows over the time, these flows resulted in large quantities of heat being stored
in rocks at shallow depths, and these rocks forms the ‘source’ of geothermal energy
extraction.
High enthalpy region – the region at which ‘highly concentrated heat flow (heat flux)’
occurs, and where the heat is available in the forms of steam and hot water (100-200°C).
These regions are suitable for ‘power generation’
Low enthalpy region – temp is low, heat warm water. Suitable for ‘heating and drying’
application.
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Geothermal energy, OTECs and Tidal energy
The Himalayan
geothermal belt,
Eastern china,
Russia, Japan, the
Philippines,
Indonesia, etc.,
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Geothermal energy, OTECs and Tidal energy
1. An aquifer (which is porous rock that can store water, and flow of water is possible
inside it), it can be accessed by ‘drilling’.
2. A cap rock to retain the geothermal fluid (seal for the fluids)
3. Heat source (three different types of heat source (i) volcano – related heat source, (ii)
sedimentary basins and (iii) hot-dry rocks).
A geothermal aquifer must be able to ‘sustain’ a flow of geothermal fluid so that even highly
porous rocks are suitable only if the pores are interconnected.
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Geothermal energy, OTECs and Tidal energy
The velocity of a fluid moving through a porous medium, ‘v’ can be described by ‘Darcy’s law’
H/L – the change in the ‘head’ per meter of distance ‘L’ along the direction of flow
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Geothermal energy, OTECs and Tidal energy
2. Indirect way – heat is extracted from the site by using heat exchangers
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Geothermal energy, OTECs and Tidal energy
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Geothermal energy, OTECs and Tidal energy
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Geothermal energy, OTECs and Tidal energy
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Geothermal energy, OTECs and Tidal energy
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Geothermal energy, OTECs and Tidal energy
Tropical ocean – surface water 25 to 27°C – deepwater below (1000m) 5°C. The difference
(around 20°C) is used to make ‘energy’ is called ‘OTEC’.
Upper layer vast ‘reservoir’ of heat held @ temp near 27°C by a balance b/w ‘the absorption of
heat (from the sun)’ and ‘the loss of heat (by evaporation, heat transfer loss and re-radiation).
Fact : on an avg day, the water near the surface absorbs more heat from the sun in one square mile
of ocean area than the heat that could be produced by burning 7000 barrels of oil.
OTEC system needs supply of ‘warm’ and ‘cold’ water with the temp diff of 20°C, and a
‘inexpensive and efficient’ heat engine for extracting work from the heat supply – heat sink
combination, and a reasonable methods for delivering the output to users.
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Geothermal energy, OTECs and Tidal energy
The Rankine (closed) cycle heat engine with a typical refrigerant as working fluid (liquid
NH3) will be boiled using warm water’s heat the vapor expand thr the turbine
cycle work condensed by cold water pumped back into the boiler.
For modest yield of output work, large quantities of heat was req, for which large boilers and
condensers were req.
2 types of OTEC process (i) Closed – cycle systems and (ii) open – cycle systems
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Geothermal energy, OTECs and Tidal energy
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Geothermal energy, OTECs and Tidal energy
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Geothermal energy, OTECs and Tidal energy
Tidal power
Use of tides (not waves) to provide energy – turbines mounted in large barrages (low dam
structures), which are artificial barriers build across a river or estuary.
Upstream tide (flood tide) flows towards the barrages are trapped. As the tide declines
level of water on the other side (downstream) of the barrages ‘reduces’ Head of water
(water body at a certain height, called ‘Head’) develops potential energy to kinetic
energy.
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Geothermal energy, OTECs and Tidal energy
Tidal power
The formation and variation in tidal height gravitational interaction b/w earth and moon/sun.
As the earth rotates in its axis gravitational force produce twice-daily rise and fall in sea
level modified by gravitational pull of the sun interaction is complex
Gravitational pull of moon draws sea on earth ‘nearest’ to moon bulge (high tide pattern)
as earth rotates, this bulge maintains two high tides per day (moon’s rotational time).
This pattern is modified by ‘pull’ of the sun.
Spring tides very high tides when sun and moon pull together in line
Neap tides low tides when sun and moon are apart (90°)
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Geothermal energy, OTECs and Tidal energy
Tidal power
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