Ammonia-Water Based Thermal Conversion Technology: Applications

in Waste Heat Recovery for the Cement Industry

Mark D. Mirolli
Chief Technology Officer
Recurrent Engineering, LLC

Abstract

Cement production is one of the most energy intensive industrial processes in the world. In many world
regions, energy cost is 50% to 60% of the direct production cost of cement. Energy cost is incurred due to
the need for large quantities of thermal heat for the kiln, calcination and drying processes and electrical
energy for operation of motors for grinding mills, fans, conveyers and other motor driven process
equipment.

As electricity prices increase, cement producers are installing energy saving devices throughout cement
plants to incrementally reduce purchased power. A major energy conservation project available to each
cement facility is utilization of the exhaust gases from preheater towers and clinker coolers to produce
electricity. Both of these heat sources are classified as medium to low temperature heat for electrical
power generation. These heat streams are well matched for use of the Kalina Cycle process for waste
heat recovery (WHR) to produce electricity.

This paper describes the conditions of typical cement plant heat sources available for utilization to
generate electricity. The sources of heat from cement plants are compared with specific heat sources
utilized in existing Kalina Cycle power plant projects. The Kalina Cycle is described for power generation
inside the fence of a cement plant facility including specific environmental and operational safety
considerations.

Cement Plant Heat Source Conditions for Power Generation

WHR utilizing cement plant exhaust gases includes two general sources from the cement process, the
suspension preheater (SP) exhaust gas and the hot air from the clinker cooler (CC) discharge. These
heat sources may be used separately or in combination for WHR power generation. These two heat
sources have different temperature levels and include suspended dust particles of different volumetric
loading levels and particle fireside characteristics. Typical exhaust gas conditions are presented in Table
1. Frequently, the SP exhaust gas is used within the cement plant for drying raw materials, which limits
the available heat for power generation. The WHR generation system design must consider the drying
requirements in the cement plant raw mill to optimize the amount of electricity generated on an annual
basis.

Gases from both the SP and CC streams are cooled in primary heat exchangers in the Kalina Cycle
process. The primary heat exchangers can be arranged in parallel with existing air-to-air heat exchangers
and/or spray towers, or as a stand-alone design that replaces air-to-air heat exchangers and/or spray
towers.

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 Table 1
Cement Plant Typical Exhaust Gas Conditions

Gas Temperature, Dust Content,

3
Gas Stream C g/Nm Comments
SP Exhaust 350 to 400 80 to 200 Dust is sometimes sticky

CC Hot Air 200 to 300 5 to 10 Small amounts of hard

(before dust large particles
removal)
CC Hot Air 200 to 300 0.03 to 0.05 Dust is small in size and
(after dust quantity
removal)

SP exhaust gas contains a large quantity of dust. The primary heat exchanger designed to remove heat
from this stream must include a dust removal system designed to control fouling of the heat transfer
tubing. The CC hot air stream prior to dust removal equipment includes a low dust loading in comparison
with the SP exhaust gas, however the dust is abrasive in nature. Hot air velocity entering the primary
heat exchanger must be maintained typically less than 6 meters per second to prevent erosion of the CC
primary heat exchanger tubing. If dust control equipment is installed ahead of the primary heat
exchanger (e.g. cyclone, electrostatic precipitator, baghouse), the hot air velocity may be increased
dependent on the effectiveness of the dust removal equipment.

Primary heat exchanger dust removal systems for both the SP exhaust gas and CC hot air streams need
to designed considering the dust properties and primary heat exchanger designs. Air blowers have been
employed in a relatively wide range of WHR application including cement plants. This is the most
effective means to control dust accumulation, however, it consumes power to provide high-pressure air
for dust removal. In some applications, impact dust removal techniques have proven successful in SP
exhaust gas applications. Mechanical hammers or rappers are used to impact tube assemblies. This
rapping mechanism shakes the dust from tubing surfaces. Alternatively, steel ball shot cleaning
systems have been successfully utilized in CC hot air streams when the primary heat exchanger is
located upstream or ahead of cement plant dust removal equipment. Specific dust removal equipment
depends on the primary heat exchanger design and the specific operating conditions of the WHR power
plant.

The SP exhaust gas may contain sulfur gases depending on the fuel used in the cement manufacturing
process. Sulfur trioxide (SO3) present in the SP exhaust gas is a precursor to sulfuric acid mist formation
in the low temperature regions of the primary heat exchanger. Sulfuric acid mist will greatly accelerate
the corrosion of heat transfer tubing. To prevent this phenomenon the primary heat exchanger design
should include gas temperatures above the sulfuric acid mist formation temperature. This will depend on
the concentration of SO3 and water vapor present in the SP exhaust gas.

Kalina Cycle Technology

The Kalina Cycle is particularly well suited for the low and medium temperature heat available in a
cement plant. It is based on the use an ammonia-water mixture working fluid. The thermodynamic
characteristics of this fluid include non-isothermal boiling and condensing. These thermodynamic
characteristics coupled with the ability to alter the ammonia-water concentration at various points in the
power plant, improves the effectiveness of heat acquisition, regenerative heat transfer and heat rejection.
Each of these improved heat transfer processes increases the power plant net efficiency resulting in a
greater amount of electricity production from a fixed heat source.

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The Kalina Cycle has proven effective in other industrial WHR applications. Previous WHR experience
with this technology covers a range of operating conditions that meet the requirements for WHR from
cement plant SP exhaust gases and CC hot air streams.

Waste Heat Recovery Project Experience

The Kalina Cycle has been successfully used in a range of WHR power plant projects including
applications in steel making, oil refinery and municipal incineration. The operating conditions of these
projects overlap the conditions required for cement plant WHR power plants. Heat sources temperatures
of up to 1650 F have been used with dust laden gases in Kalina Cycle power plants. Retractable
sootblowers have been used in municipal incinerator applications to control particle buildup on heat
transfer surfaces. The same conventional sootblowing equipment has also been successfully used in
cement plant WHR power plants based on conventional Rankine cycle or steam cycle power plants. A
system of retractable sootblowers used in a cement plant WHR project is shown in Figure 1.

Figure 1 Retractable Sootblowers in a Cement Plant WHR Facility

The Kalina Cycle primary heat exchanger is a once-through design without the need for thick walled
steam drums for high-pressure liquid-vapor separation, or primary heat exchanger blowdown systems to
maintain the working fluid quality. A water treatment system is not required to provide a continuous
makeup stream of working fluid, as is the case in a steam cycle power plant with water used as the power
cycle working fluid. Ammonia-water is directly heated in the primary heat exchanger of a Kalina Cycle
plant. There is no need for an intermediate heat transfer fluid within the power plant design to transfer
heat between the exhaust gases and the power cycle working fluid. This improves the WHR plant
efficiency thereby increasing the electrical generation, and it reduces the plant complexity and capital
cost. This type of WHR primary heat exchanger design has been used successfully in Kalina Cycle
power plants utilizing exhaust gases from municipal fluidized bed incineration (1650 F, dust laden) and
utilizing exhaust gases from a natural gas fired combustion turbine (1010 F). All forms of particulate or
dust control are applicable in the primary heat exchanger of a Kalina Cycle WHR power plant.

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Canoga Park Demonstration Project

Figure 2 Canoga Park Demonstration Plant

The Kalina Cycle process was first demonstrated in a 3 MW project near Canoga Park, California. The
plant ran through a series of test campaigns from 1992 through 1997 to prove the following results:

The plants thermodynamic performance was confirmed including temperature-enthalpy data for
ammonia-water mixtures.
Changing and controlling the composition of the working fluid mixture. The working fluid
containing 70% ammonia by weight was converted into intermediate solutions of 42%, 30% and
96% ammonia in different parts of the Distillation and Condensation Subsystem (DCSS) and then
re-established in a precise, controlled manner.
The plant operation was safe, stable and reliable. Startup and shutdown were accomplished
using remote, automated control.
All materials and equipment were proven to be compatible with the ammonia-water working fluid.
Ammonia was handled with relative ease and in an environmentally benign manner. Operational
safety procedures were successfully established.

The power plant design for the demonstration plant comprises a primary heat exchanger, a vapor turbine
generator and a Distillation/Condensation Subsystem (DCSS). Each of these primary subsystems is
included in the design of a cement plant WHR facility.

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The Canoga Park demonstration plant design includes temperatures and pressures well in excess of the
conditions required by any cement plant WHR facility. The turbine inlet ammonia-water temperature and
pressure are 960 F and 1600 psia, respectively. The plant was designed to capture waste heat from flue
gases at 1010 F. A photograph of the facility is included as Figure 2 and a schematic of the Kalina Cycle
process is included as Figure 3.

Figure 3 Canoga Park Process Schematic

Kalina Cycle WHR for Cement Plant Applications

A typical process schematic for a Kalina Cycle waste heat recovery power plant for a cement facility is
shown in Figure 4. This system is a similar process to the Canoga Park demonstration plant operating at
significantly less severe thermodynamic conditions in comparison with Canoga Park. In most cement
plant WHR applications, the highest temperature within the power plant will be 100 to 300 F lower than
experienced in Canoga Park. Correspondingly, in most cement plant WHR applications, the maximum
operating pressure within the power plant will be 25 to 50% less than experienced in Canoga Park.

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The heat sources are the preheater exhaust and the clinker cooler exhaust gases. Two primary heat
exchangers referred to as Heat Recovery Vapor Generators (HRVGs) are provided, one for the preheater
exhaust (HRVG-1) and one for the clinker cooler exhaust (HRVG-2). A rich mixture of water and ammonia
is boiled and superheated in the HRVGs, using both units for the evaporation but just the hotter preheater
exhaust for superheating and (often) just the cooler exhaust for preheating if the preheater exhaust has
acid condensation limits. The superheated vapor is then expanded through a back-pressure turbine. The
turbine exhaust is recuperatively cooled and diluted with the lean (low in ammonia concentration) bottoms
from a vapor separator/demister, this allows it to fully condense in the low-pressure condenser (LPC), at a
lower pressure than if left undiluted. After pumping to an intermediate pressure (sufficient to condense the
HRVG concentration), most of the diluted fluid is partially boiled and sent to the vapor separator/demister
through recuperative heat exchangers. The rest is mixed with the high ammonia concentration vapor
stream from the vapor separator/demister. This process restores the working fluid to the optimum
ammonia-water concentration for the heat acquisition stage of the cycle. The working fluid is then
condensed in the high-pressure condenser (HPC) and pumped through the HRVGs.

Preheater
Exhaust
Turbine

HRVG-1

Air Cooler
Exhaust

DCSS

HRVG-2

HPC LPC
Kalina Cycle
Conceptual Flow Diagram
System 1-2

KCS1-2 cool ant

Figure 4 Cement Plant WHR Process Schematic

The Distillation and Condensation Sub-System (DCSS) consists of the demister/separator, recuperative
heat exchangers, HPC and LPC condensers and control system. It provides the vital function of
establishing the high ammonia-water concentration for the heat acquisition stage and a low ammonia-
water concentration for the condensation stage.

The DCSS technology is a key component of the high efficiency of a Kalina Cycle plant for industrial
waste heat applications. This sub-system was first used at the Canoga Park demonstration plant. As
noted above, the distillation process leans out (i.e. lowers the ammonia concentration of) the turbine
exhaust stream just before it enters the low-pressure condenser. Since a leaner mixture has a lower
saturation pressure at a given temperature, the exhaust stream will then condense at a lower pressure. A

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lower turbine exhaust pressure increases the pressure expansion of the working fluid through the turbine,
thus maximizing turbine power.

All heat input for the distillation process is acquired from the turbine exhaust stream. This process is
enabled by the variable-temperature boiling and condensing property of an ammonia-water mixture. This
process will not work for pure working fluids such as water or hydrocarbons because these fluids boil and
condense at a constant temperature.

The second stage of the DCSS restores the working fluid to the original ammonia-water concentration. A
feed pump then directs this fluid back to the HRVGs to repeat the process in a closed-loop arrangement.

The HRVGs are simple heat exchanger designs that do not require steam drums. This allows fast cycling
of the HRVG during startup and shutdown and increases the flexibility of the heat exchanger design to
minimize tube fouling caused by sticky dust deposits. Proven tube cleaning and dust removal systems are
part of the HRVG design. The ammonia-water working fluid is heated directly by the cement plant
exhaust gases in the primary heat exchanger. There is no need for an intermediate heat transfer loop.

A mixture of ammonia and water is used as a working fluid for several reasons:

First, the use of a lighter component (ammonia), allows efficient use of the waste heat stream at a
higher pressure by causing boiling to start at lower temperature.

Second, the use of a mixture allows the composition to be varied through the use of distillation,
resulting in a richer composition for the boiler, and a leaner composition in the low-pressure
condenser. The variable temperature boiling process of ammonia-water reduces losses in heat
transfer processes throughout the power plant, thereby increasing the efficiency of the power
cycle.

Third, because of the similar molecular weights of ammonia and water (17.03 vs. 18.015) the
ammonia-water vapor behaves virtually the same as steam, which allows the use of standard
steam turbine components.

Fourth, standard materials can be used. Carbon steel and standard high-temperature alloys are
acceptable for handling ammonia. Only the use of copper and copper alloys is prohibited in
ammonia service.

Fifth, ammonia is readily available and relatively inexpensive.

Sixth, ammonia is not harmful to the environment.

Seventh, there are proven safety procedures for the handling and use of ammonia in industrial
plant applications including Kalina Cycle WHR facilities.

Additional project design and operating features of the Kalina Cycle for WHR power plant applications
that are especially applicable for cement plant projects include the following:

Design of the WHR power plant is such that cement production will not be interrupted in the event
the power plant is shutdown, or trips off-line.

Freeze protection is not required for the working fluid.

There is no power plant liquid effluent (no boiler blowdown for once-through vapor generators).

The plant capacity will automatically follow the heat source deviation by a sliding pressure
operation mode.

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Environmental and Safety Considerations

All vents, drains and safety valve discharges containing ammonia are directed to a water filled blowdown
tank. A perforated header inside the tank discharges into a pool of water where the ammonia is
absorbed. An ammonia concentration in the tank is maintained below about 10% ammonia by weight by
partially draining the tank and refilling it with fresh water. The drained fluid is typically sold as a byproduct
for use as a fertilizer or for industrial cleaning fluid manufacture. There is no intentional release of
ammonia from the WHR power plant.

Ammonia poses little fire and explosion threat. Ammonia will not support combustion without a source of
ignition. An ammonia-water solution can be directly heated in the WHR power plant primary heat
exchanger without creating a safety risk, thereby improving the WHR plant performance and capital cost.

Ammonia will not harm the environment. It is produced as a decomposing byproduct from natural
sources. It is part of the earths nitrogen supply cycle, and therefore does not contribute to global
pollution or global warming. It is much lighter than air and, therefore, easy to disperse in the atmosphere.
In the future, ammonia use will become Best Available Control Technology (BACT) in WHR power
generation from low and medium temperature heat sources such as cement kilns. Organic fluids used to
date in these types of power plant systems are contributors to photochemical smogs and depletion of the
earths ozone layer. Organic fluids are flammable and may represent a chemical explosion hazard. In
the event of an accidental spill, organic fluids represent a hazard to local ecosystems.

Summary

The Kalina Cycle is an energy efficient technology available for electricity generation utilizing cement
plant process exhaust gases. This technology is proven in other WHR industrial applications for the range
of conditions typical in most cement plant facilities. This technology improves WHR plant efficiency
thereby increasing electrical generation, and it reduces the plant complexity and capital cost. The primary
heat exchanger design for these power plants is a major consideration to achieve reliable, stable
operation of the WHR power plant system. The fireside effects due to dust particles and sulfur gases are
controllable with proper primary heat exchanger design and operation.

References

Mirolli M. D., The Kalina Cycle for Cement Kiln Waste Heat Recovery Power Plants, Proceedings of the
2005 IEEE-CIC/PCA Cement Industry Conference, May 15-20, 2005.

Mlcak, H. A., An Introduction to the Kalina Cycle, Proceedings of the International Joint Power
Generation Conference, Book No. H01077-1996.

Mirolli, M. D. and Leibowitz, H., First Kalina Combined Cycle Plant Tested Successfully, Power
Engineering, May, 1997.

Iiyoshi, T. et. al., Introduction of a Power Generating System by Low Temperature Waste Heat Recovery
(Kalina Cycle Power Generating System), 2000.

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