Thermoelectric Electricity Generation From Low Temperature Flue Gas Stream

Abstract:

Almost 20-50% of industrial energy input is lost to environment in the form of waste heat as hot exhaust
gases, cooling water, and heat lost from hot equipment surfaces and heated products contributing 1/3 rd to
greenhouse gas emissions. This waste heat arises due to both equipment inefficiencies and
thermodynamic limitations of the equipment and processes. This lost or waste energy is estimated to be
over 10 quads/yr., an amount equipment to more than 1.72 billion barrels of oil or 127 days worth of
imported crude oil supply. As the industrial sector continues efforts to improve its energy efficiency,
recovering waste heat losses provides an attractive opportunity for an emission free and less costly energy
resource. The waste heat recovery market is expected to grow at a CAGR of 6.5% over the next five
years to reach $53,120 million by 2018. Various technologies, including technologies, are being
considered to recover process waste energy to useful electrical energy. Thermoelectric (TE) materials
produce electric current when joined together and subjected to a temperature difference across the
junction. This property makes it possible to produce direct current electricity by waste heat on one side of
a TE material, while exposing the other side to lower or ambient temperature surroundings.

Keywords:
Thermoelectric generator, Waste low grade heat, Seebeck effect,

Introduction:

Non-renewable electricity generation and a number of manufacturing processes reject large quantities of
energy into the atmosphere each year in the form of waste heat. This waste heat arises due to both
equipment inefficiencies and thermodynamic limitations of the equipment and processes and is typically
unrecoverable using conventional technologies because of the relatively low temperatures (usually below
450 F or 232 C ) that the heat is rejected at. This 60% of uncovered waste low quality heat has less
thermal and economic value than high temperature heat, it is ubiquitous and available in large quantities.
Waste heat has lower utility that is having a lower exergy or higher entropy. This large volume of low
grade waste heat presents significant opportunity for new and more effective energy recovery
technologies to capture interest and market share, especially as energy prices climb and concern climate
change affects regulatory policy on process efficiencies.
One potential option for the converting low grade waste heat into electricity is to use a thermoelectric
generator, or TEG. A TEG is solid semiconductor state device that converts heat into electricity by the
Seebeck effect. TEGs have recently emerged as viable electricity generators because of improved
thermodynamic efficiencies and higher survivable operating temperatures.

TE materials available prior to about 1995 produced thermal-to-electric conversion efficiencies in the 2%
to 5% range and were only used in small niche applications. However, recent significant advances in the
scientific understanding of quantum well and nanostructure effects on TE properties and modern thin
layer and nano-scale manufacturing technologies have combined to create the opportunity of advanced
TE materials with potential conversion efficiencies of over 15%. The advent of these advanced TE
materials offers new opportunities to recover waste heat more efficiently and economically with highly
reliable a relatively passive systems that produce no noise and vibration.

Uses Of Waste Flue Gas:

Low grade waste heat can be used for a number of processes, and common uses include preheating
combustion gases, heating and cooling buildings, and providing heat to industrial reactions or
manufacturing processes. Typically recycling waste for processes is more valuable than producing
electricity, but recycling can require significant changes and in many cases simply is not practical.
Electricity production from waste, on the other hands, is a stand-alone process that produces a universally
tradable community. Thus, electricity production is smart alternatives when process recycling cannot be
implemented. Organic Rankine cycles (ORC), Striling cycles, or other thermodynamic engines, such as a
TEG, can be used to convert waste heat into electricity.

Thermoelectric Principles:

A) Thermoelectric Power Generation:

Fig. 1 : Seebeck Effect

Thermoelectric Power Generation is based on Seebeck effect. The Seebeck effect is a phenomenon in
which a temperature differences between two dissimilar electrical conductors or semiconductor produes a
voltage difference between the two substances. When is applied to one of the two conductors or
semiconductors, heated electrons flow toward the cooler one.

The simplest TEG consists of a

thermocouple consisting of n-type (materials with excess electrons) and p-type (materials with deficit of
electrons) elements connected electrically in series and thermally in parallel. Heat is input on one side and
rejected from the other side, generating a voltage across the TE couple. The magnitude of the voltage
produced is proportional to the temperature gradient.
B) Thermoelectric Heating And Cooling

Fig. 2: Peltier Effect

Thermoelectric Heating And Cooling is based on the Peltier effect. The Peltier effect is a temperature
difference created by applying a voltage between two electrodes connected to sample of semiconductor
material. When electric input is applied to a thermocouple, electrons move from p-type material to n-type
material absorbing thermal energy at the cold junction. The electrons dump their extra energy at the hot
junction as they flow from n-type back to the p-type material through the electrical connector. Removing
heat from the hot side will drop the temperature on the cold side rapidly, the magnitude of the drop
depending on the electric current applied.

Efficiency Of Thermoelectric Materials: Figure Of Merit (ZT)

Good TE materials should have the following characteristics:

1) High electrical conductivity to minimize Joule heating (rise in temperature from resistance to electric
current flowing through it)
2) Large Seebeck coefficient for maximum conversion of heat to electrical power or electrical power to
cooling performance
3) Low thermal conductivity to prevent thermal conduction through the material.
These three properties are commonly called Figure Of Merit (Z) which is defined as
2
Z = /
Where
-1
is the Seebeck coefficient of the material (voltkelvin ),
-1
-1
is the electrical conductivity of the material (amperevolt meter ), and
-1
-1
is the thermal conductivity of the material (wattmeter kelvin )

Fig. 3 : Figure Of Merit

Efforts To Increase Figure Of Merit:

Fig. 4:Efficiency as function of temperature difference

Most efforts to increase ZT have centered about finding a way to decrease the thermal Conductivity. The
thermal conductivity of any solid is a sum of the thermal conductivity of the lattice, due to phonon
transport, and the electric thermal conductivity, due to the transport of charge carriers. Most
thermoelectric materials are also semiconductors, however. For many semiconductor materials, the
electric thermal conductivity, which is directly proportional to the electric conductivity, is a substantial
portion of the overall thermal conductivity.
Though the thermal and electric conductivity are not entirely independent, the ratio of thermal to electric
conductivity can still be decreased by scattering the phonons responsible for heat transport through the
lattice. Phonon scattering can be achieved without altering the ability of the electrons to pass through,
thereby lowering the / ratio.
Both theoretical and experimental research is exploring phonon scattering as an effective method of
reducing the thermal conductivity of thermoelectric materials, and thereby increasing ZT. Research is
ongoing to increase thermoelectric performance in bulk materials. In addition, nanostructured materials
have been found to have increased thermoelectric performance compared to their bulk alloys.

Thermoelectric Materials:

A) Bismuth chalcogenides and their nanostructures:

Materials such as

Bi 2 Se3 and

Bi 2 Te 3 comprise some of the best performing room temperature

thermoelectrics with a temperature-independent thermoelectric effect, ZT, between 0.8 and 1.0. Nano
structuring these materials to produce a layered superlattice structure of alternating

Sb 2 Te 3

and

Bi 2 Te 3 layers produces a device within which there is good electrical conductivity but perpendicular
to which thermal conductivity is poor. The result is an enhanced ZT (approximately 2.4 at room
temperature

for p-type).

B) Lead telluride
Thallium doped lead telluride alloy (PbTe) achieves a ZT of 1.5 at 773 K. Sodium doped PbTe have ZT
value of 1.4 at 750 K and ZT 1.8 at 850 K in sodium-doped PbTe1-xSex alloy. Lead telluride to convert 15
to 20 percent of waste heat to electricity, reaching a ZT of 2.2
C) Inorganic clathrates
Inorganic clathrates have a general formula AxByC46-y (type I) and AxByC136-y (type II),
in these formulas B and C are group III and IV atoms, respectively, which form the
framework where guest atoms A (alkali or alkaline earth metal) are encapsulated
in two different polyhedra facing each other.

D) Silicides
Higher silicides display ZT levels with current materials. They are mechanically and
chemically strong and therefore can often be used in harsh environments without
protection.
E) Tin selenide

Tin selenide (SnSe) has a ZT of 2.6. This is the highest value reported to date.

F) Nanomaterials and superlattices

Nanostructured

Bi 2 Te 3 / Sb2 Te 3

superlattice thin films, other nanomaterials show

potential in improving thermoelectric properties. Another example of a superlattice

involves a PbTe/PbSeTe quantum dot superlattices provides an enhanced ZT
(approximately 1.5 at room temperature) that was higher than the bulk ZT value for
either PbTe or PbSeTe (approximately 0.5).

Industrial Waste Heat Recovery:

The quality of waste heat differs from industries to industries. Waste heat stream composition is very
important since it determines heat capacity, thermal conductivity, phase change temperatures, and
corrosiveness. The potential industrial scenario is necessary since the application temperature limits the
utility of thermoelectric (TE) devices; the delta T (hot side vs. cold side) determines the TE devices
efficiency; and the waste heat source composition will determine corrosion, erosion, scaling, fouling and
other effects, dictating the demands on the hot-side material composition and the heat transfer surface
designs.

Table 1: Thermoelectric waste heat opportunities in the U.S. industries

Engineering Challenges:

Older bulk thermoelectric materials (i.e., Bi2Te3, PbTe, and SiGe materials) generally have low
ZT value ~ 1 & very low conversion efficiencies of only 3-6% which cannot meet industrial
waste energy recovery sufficiently. Hence, advanced TE materials must be developed & having
characteristics like greater ZT, long term stability at industrial operating conditions, low material
and fabrication costs, better thermal, chemical & structural stability, etc.

New device engineering and fabrication techniques must be developed that enhance efficiency,
reliability, and power output or cooling capacity while maintaining low costs. The thermoelectric
device (thermocouples, heat exchange attachment, wiring, interconnections, etc.) must be
engineered in a manner that allows for low-cost large-quantity production. The TE device
innovations must be compatible with the high-performance heat exchange/transfer technologies
that provide the necessary high interface heat fluxes in miniaturized systems. TE device

manufacturing encounters many of the same challenges as fuel cell development and microchannel heat exchanger and reactor development.

The thermoelectric generator system consists of the thermoelectric device, all heat exchange
technology (hot- and cold-side) necessary to maintain the operating conditions appropriate
for the device, and an electronic volt/ampere control module. The TEG system must be
capable of installation and operation without economically offsetting modifications or new
large capital requirements to existing plant equipment and processes.

Alternative Techniques:

There are significant waste heat opportunities at process flow temperatures near 150C (~302 F), such as
in industrial water/steam boiler applications and ethylene furnaces. The largest waste energy opportunity
is in water/steam boilers in the commercial and industrial applications (~1,170 TBtu/yr collectively).
Unfortunately, these temperatures are generally too low to efficiently employ thermoelectric power
generation. An alternative technology, called piezoelectric power generation (PEPG), is emerging as a
low-temperature power generation technology that can directly convert heat into electrical energy. This
technology operates on the theory of an oscillatory liquid-to-gas expansion within a closed chamber
stressing a piezoelectric thin-film membrane, thereby creating a time-dependent voltage output. It
operates most effectively in the 100C to 150C temperature range, so it would be best suited for waste
heat recovery in water/steam boilers and ethylene applications (at 150C). There are other configurations
that are intended to capture mechanical energy directly and convert it into an electrical signal.

PEPG technology is currently fielded in a thin-film membrane configuration that is only about 1%
efficient in converting heat to electrical energy. There are many technical challenges associated with this
early stage power generation technology including:

Low conversion efficiency

High internal impedance

Requirement for oscillatory heat loads

Oscillatory electrical signals

Complex oscillatory fluid dynamics within the liquid/vapor chamber

Difficulties in obtaining high enough oscillatory frequencies

Long-term reliability and durability

Very high cost ($10,000 /W)

The technology usually employs a common piezoelectric oxide material, lead zironate titanate (PZT), in
the active membrane. PZT is used in many microelectromechanical systems (MEMS) applications
because of its high piezoelectric and electromechanical coupling coefficients. Different piezoelectric
materials and device materials are being investigated to improve performance and manufacturability, and
lower the cost of PEPG devices. Current devices can operate at ~100 Hz, but the real need is to operate
near 1000 Hz. It is also clear that similar heat transfer interface challenges will exist at the hot- and coldsides in PEPG systems as in TEG systems. At the lower temperatures applications, there will be less
temperature driving potential to transfer the large amounts of heat involved. This will lead to larger heat
exchange systems than in the higher temperature heat recovery applications addressed by TEGs if gas
flows are used on the PEPG system hot-side. In these applications (150C), if liquid or two-phase flow
streams can be used instead of gas flows, then much better heat transfer conditions on the PEPG hot side
can be achieved, which will invariably lead to higher PEPG system performance.
The low energy conversion efficiency of PEPGs can theoretically be overcome by cascading a single
device into a multiple number of devices in series thermally and outputting electrically in parallel.
However, PEPG cascading has not been demonstrated to date and there are technical challenges
associated with this approach, not the least of which is controlling heat losses at each stage. If PEPG
cascading can be accomplished and cost-effectively demonstrated, then energy conversion efficiencies of
the multi-stage PEPG stack could be 8-10% or even higher. This provides a strong opportunity to recover
a significant fraction of the large amount of waste energy available at ~150C in industrial water/steam
boilers and ethylene applications.

Currently, Defense Advanced Research Projects Agency (DARPA) is conducting R&D to advance this
technology and is certainly a viable energy conversion technology that DOE could invest in to accelerate
its development and demonstration. Industrial interest in this technology should be fostered as much as
possible.

Conclusion:

Energy content of waste streams was evaluated based on reference temperatures of 77F [25C] and
300F [150C]. Calculations based on a 77F [25C] reference reflect maximum heat recoverable by
cooling heat streams to atmospheric temperatures. The 300F [150C] reference reflects the typical
practice of cooling exhaust gases to no less than 300F (150C) in order to prevent flue gas condensation.
Based on a reference temperature of 77F [25C], waste heat losses via sensible and latent heat contained
in exhaust gases studied in this report are about 1.5 quadrillion Btu/yr. Only about 160 TBtu/yr are
estimated as potentially recoverable energy based on a reference temperature of 300F [150C].
Work potential based on Carnot efficiency for energy conversion (mechanical or electrical) was also
evaluated in order to better compare waste heat with different exhaust temperatures. Based on a 77F
[25C] ambient reference temperature, the work potential of all the waste heat studied is about 600
TBtu/yr. Despite the very low Carnot efficiency for low temperature energy conversions, about 75% of
the work potential is contained in low temperature waste heat streams (i.e., at less than 450F [230C]).
This is a result of the very large mass flow rate of these low temperature waste heat streams.

Major issued about TEGs:

> ZT ~ 1 material will not provide the thermal efficiency and system costs to be the long term solution to
industrial scale waste heat recovery. However, they can serve as prototype system components to
demonstrate TEG waste heat recovery concepts and provide lessons learned for industrial applications
where heat exchange degradation, thermal cycling, vibration and other deleterious operating conditions
are commonly encountered.
> Advanced TE materials having ZT ~ 2 properties that have recently been developed and characterized
and new advanced TE materials with ZT ~ 4 envisioned in the long-term future will strongly enhance

TEG commercialization by providing the thermal conversion efficiencies needed to make TEG
economically attractive. The 20% energy conversion efficiency appears possible in advanced TEG
systems operating at hot-side temperatures of ~ 1000K.
> Waste heat applications with large mass flow rates, high temperatures and no on-site opportunities for
thermal exchange with other fluids/solids have been identified (e.g., glass furnaces, primary aluminum
cells, and aluminum furnaces). Integrating TEG systems into the exhaust manifolds of these processes is
practical. The development of these applications can provide the foundation for a new industry dedicated
to recovering the energy losses associated with industrial manufacturing.

> Enhanced TEG performance (ZT ~ 2 and >15% thermal efficiency) will provide for a more attractive
business case, both for the TEG developer and the end-user. Higher efficiency levels will produce more
power output at higher power density, thereby creating a stronger value proposition for the industry (i.e.,
more power output will be possible from smaller devices and systems).

Reference:
1. Jacob G. Latcham, MIT: Heat Exchanger Design for Thermoelectric Electricity Generation from
Low Temperature Flue Gas Streams, 2009.
2. http://en.wikipedia.org/wiki/Waste_heat_recovery_unit
3. http://en.wikipedia.org/wiki/Thermoelectric_materials
4. Engineering Scoping Study of Thermoelectric Generator Systems for Industrial Waste Heat
Recovery, November 2006, US Department of Energy.
5.

Waste Heat Recovery: Technology & Opportunities in U.S. Industries, BCS, March 2008.

6. http://scholarworks.wmich.edu/cgi/viewcontent.cgi?article=1493&context=masters_theses

7. https://tu-dresden.de/die_tu.../2012_06_EEVC_II_Dresden_TEG.pdf