How Thermal Oxidation Can Increase the Sustainability of a Chemical
Plant
Jon Hommes, Engineer, Durr Systems, Inc.
Installing new production processes, or upgrading and expanding existing lines
today requires a review of the expected emissions. The right emission control
system for Hazardous Air Pollutants (HAPs) and Volatile Organic Compounds
(VOCs) can help efficiently and economically dispose of these environmentally
hazardous wastes. Over the last 20 years, as emission limits have tightened
and authorities have taken a more “holistic”, plant-wide approach to air permits,
the trend in CPI has been to collect multiple waste streams plant-wide for
control in a single thermal oxidation system, despite the required additional
source ducting and piping. This trend has been driven by an array of factors,
including:
• Rising fossil fuel prices
• Tightening of emission limits for VOCs, HAPs, NOx and CO
• Goals for the reduction of a plant’s carbon footprint
• Increasing cost for disposal of organic waste liquids
• Minimizing the number of control systems to be maintained and points
of emission monitoring and testing
All of these are key for companies increasingly commited to energy efficient,
sustainable production. The benefits of a single, centralized thermal oxidation
system can be best illustrated with a case study of the experience of a plant
that recently added emission controls to many existing production processes.
Two types of thermal oxidizers are most frequently applied in the chemical
process industry: Regenerative Thermal Oxidizers (RTOs) and Direct Fired
Thermal Oxidizers (DFTOs), also known as Afterburners. RTOs offer high
thermal efficiency and very low fuel requirements for plants that generate dilute
air streams contaminated with low concentrations of VOCs and HAPs.
However, a DFTO is the best choice when:
• Production processes demand steam energy
• Required destruction efficiency is greater than 99.5%
• Highly caloric off gases with low oxygen must be handled
• High loading of halogenated or sulfurous compounds are expected (acid
generators)
• Destruction of waste liquids is needed
Dürr Systems, Inc.
40600 Plymouth Road
Plymouth, MI 48170-4297
Phone +1 734-459-6800
Fax +1 734-459-5837
www.durr.com
Many excellent guides and articles address the selection process between
different types of oxidizers. This paper focuses on the DFTO exclusively.
A company manufacturing organic intermediates for the pharmaceutical and
fertilizers industry decided to install a direct fired thermal oxidizer system to
handle all liquid and gaseous waste streams from their many small to mid-size
process reactors and storage tank vents. The DFTO is designed to handle a
wide range of wastes including organic compounds containing halogens, sulfur
and nitrogen.
The system consists of the required liquid pipe trains and storage tanks,
process off gas pipe trains including explosion protection equipment, oxidation
chamber, fire tube waste heat steam boiler, economizer, scrubber for acid gas
removal, selective catalytic reduction (SCR) system for NOx removal, an
induced draft system fan and stack including emission monitoring system.
Components in a modular DFTO system can be selected based upon the
waste stream contaminants
Waste Liquids and Off Gas Sources
The liquid wastes are accumulated from a number of sources across the plant
and collected in a storage tank. The small storage tank was sized to
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accommodate the effluents from periodic tank cleaning processes. At this
particular plant, all of the waste liquids are purely organic and have a
consistent high caloric value which allows them to be fired directly through the
thermal oxidizer’s dual fuel burner system. After start-up, these systems can
run entirely on the waste liquid fuel. Although not needed at this facility, a
second system is sometimes used to collect liquid wastes with low or
inconsistent caloric value or high water content. These wastes are atomized
into the oxidation chamber adjacent to the burner through secondary injection
lances.
In addition to the liquid wastes, a total of six process off gas streams are
controlled by the thermal oxidizer system. Each off gas is handled by an
independent control train and injected separately into the oxidation chamber.
One stream is drawn from nitrogen-blanketed storage tanks using a blower,
designed to handle potentially explosive gases, to maintain a slight negative
pressure. The remaining streams come from process reactors under pressure
and can be routed to the oxidation chamber without blowers. The volume of off
gas and VOC caloric content of each stream is highly variable, especially for
several batch reactors and for the storage tanks which vent the most VOC
during filling operations. These large variations of flow and loading lead to the
first major benefit of a single, centralized DFTO system.
Multiple skid-mounted off gas piping control trains
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During preliminary engineering of the emission controls, consideration was
given to multiple, smaller DFTO systems installed local to each process gas
source. This arrangement has the advantage of minimizing the cost of the off
gas collection system duct work and keeping each process fully independent.
However, as the off gas sources were analyzed, it was determined that each
DFTO would need to be designed for the peak off gas volume and caloric
content required for that source under startup or upset conditions resulting in
large oxidizer size. Furthermore, the much lower “normal” off gas flow is then
difficult to handle efficiently in the large oxidizer. Designing for this high
turndown is especially challenging for the several batch reactor processes.
Bringing all of these off gas streams to a single, centralized DFTO makes it
possible to design for the peak VOC loading on several, but not necessarily all,
processes simultaneously, reducing overall system size and capital cost, while
improving turndown and DFTO efficiency under normal operation. The
availability of the organic waste liquids to the centralized DFTO also has a
stabilizing effect on operation as the storage tank allows injection of liquids to
cease during periods of maximum off gas loading (while collection in the tank
continues) and to resume providing supplemental heat during periods of low off
gas loading. The overall impact of the centralized DFTO is a significant
reduction in natural gas (or other supplemental fuel) usage and thus the plant’s
utility budget. By minimizing supplemental fuel usage, a corresponding
reduction in the plant’s carbon footprint is achieved. Whether greenhouse gas
(GHG) emission reductions are mandated, as they are in Europe, or whether
they are voluntary, this is an increasingly important consideration for many
companies.
Process Steam
Many chemical plants generate and use steam on site for various process and
heating requirements. The flue gas from a DFTO oxidation chamber is a
source of high quality waste heat at 1600 to 2200˚F that is easily convertible to
saturated or superheated steam to supplement the facility’s gas, oil or coal-
fired boilers and reduce their fossil fuel usage. To do this, the refractory lined
oxidation chamber of the DFTO is simply transitioned to mate up to the boiler
inlet. Numerous considerations affect the boiler design and selection including:
• The desired steam pressure
• Requirement for superheated steam
• Presence of halogens or sulfur that generate acid gases
• The presence of silicon, phosphorous, metals and other dust-forming
compounds
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In this case, the system includes a fire tube waste heat boiler to generate
medium pressure saturated steam, followed by a super-heater and an
economizer for preheat of boiler feed water. High concentrations of
hydrochloric and hydrobromic acid in the oxidizer flue gas result in a design
that limits the heat recovery in the economizer to keep the outlet temperature
above acid dew point under all operating scenarios. In addition, due to the
distance from the facility’s main boiler house, the system included a boiler feed
water tank with redundant pumps and a deaerator for returning condensate.
Fire tube style, single pass waste heat boiler
Once again, a single, centralized DFTO when compared to multiple local units
is significantly more beneficial. To achieve the same steam production, the
capital cost is much lower for a single waste heat boiler system with high
utilization than for multiple boilers connected to localized DFTOs. Waste heat
boilers for localized DFTOs must be designed and sized for the peak flow and
heat load from each oxidizer but will normally operate at just a fraction of that
design capacity. It is obvious that the boilers themselves are capital intensive,
but a single centralized waste heat boiler also minimizes installation costs
associated with piping for boiler feed water, steam supply and blow down. The
number of boiler startup and shutdown cycles is reduced, increasing the
longevity of the equipment, and minimizing the time demands on boiler
operators. The net effect is an improvement in the pay back that justifies
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waste heat recovery as steam. By choosing to recover waste heat, the plant
further reduced their overall fossil fuel consumption and carbon footprint.
Acid Scrubber
After exiting the economizer, the flue gas is directed to a quench and acid
scrubber. The quench cools and saturates the flue gas stream with water
spray nozzles and flooded walls. The quench discharges the flue gas and
water into the base of a vertical flow, packed column scrubber where HCl, Cl2,
HBr, Br2, HF and SO2 are absorbed and neutralized with NaOH solution. The
scrubber removes over 99% of these contaminants, however, taller columns
and multiple stages can be used to achieve greater than 99.9% removal. 50%
NaOH is available as a utility at this facility and feeds a day-tank from which
redundant pumps dose it into the recirculated scrubber wash water to control
the pH.
The waste liquid and three of the six off gas streams currently contain
halogens requiring scrubbing downstream of the oxidizer with the vast majority
coming from methylene chloride in the waste liquid. Prior to installation of the
new DFTO system, these halogenated liquids were transferred to tanker trucks
and disposed of off site at significant expense ($0.20 to $0.50 per gallon). As
with the waste heat boiler, adding a scrubber to the single centralized DFTO
system has a significant capital cost advantage over scrubbing on multiple
smaller units.
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Typical quench and acid scrubber after a DFTO
Selective Catalytic Reduction of NOx
In recent years, regulatory authorities have focused more and more on
reducing NOx emissions from combustion processes, and oxidizers are no
exception. In the case of a boiler or process heater, the majority of NOx
emissions form as “thermal NOx” from N2 in the flame front of gas and oil-fired
burners. In the case under study here, the vast majority of the expected NOx
comes from the oxidation of amines and other VOCs containing nitrogen in the
plants off gases and waste liquids. Several alternative approaches for NOx
reduction were evaluated, including non-catalytic reduction in the oxidation
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chamber, before selective catalytic reduction (SCR) was selected based on the
high conversion efficiency required to meet the very low emission targets.
SCR also offers the advantage that the catalyst used to reduce NOx also
favors the destruction of trace dioxins and furans formed during the oxidation
of chlorinated compounds.
Diagram of a Selective Catalytic Reduction (SCR) system for NOx control
Because the flue gas exiting the scrubber is saturated and contains trace
acids, the SCR system begins with a pre-heater module to raise the flue gas
temperature above its dew point by mixing a small volume of hot air
recirculated from downstream. This module is constructed in alloys resistant to
chloride corrosion. The DFTO system’s redundant draft fans follow the pre-
heater and are operated on variable frequency drives to maintain a pressure in
the oxidation chamber slightly negative to atmosphere. The flue gas then
enters a recuperative heat exchanger that recovers heat from the SCR outlet
(the reduction process is exothermic) to bring the flue gas up to reduction
temperature. Finally, an aqueous ammonia reducing agent is sprayed into
stream, metered precisely to match the measured incoming NOx, before the
flue gas enters the catalyst beds where greater than 95% of the NOx is
converted to N2 and H2O. The flue gas then passes through the other side of
the heat exchanger on its way to the system stack where it exhausts to
atmosphere at about 200˚F. Continuous emissions monitoring equipment in
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the stack, as required by the plant’s air permit, tracks exhaust concentrations
of total hydrocarbon, hydrochloric acid and NOx to confirm proper operation of
the system.
The low NOx emission required for this system was another factor in the
selection of a single, centralized DFTO system over multiple system. The SCR
system is capital intensive, including expensive precious metal catalyst, heat
exchanger, and flue gas analyzers and strongly favored installing just one.
Conclusion
For this manufacturer of organic chemicals operating many smaller processes,
a single centralized thermal oxidizer system was the most cost-effective path to
expand production while meeting new emission controls requirements. The
resulting DFTO system benefited them by:
• Maximizing the destruction efficiency of VOCs and HAPs
• Reducing NOx emissions well below their permit limits
• Eliminating operating expenses for off site waste liquid disposal
• Reducing plant-wide fossil fuel demand by using the caloric value of
their wastes to generate steam
• Minimizing maintenance costs by installing just one system
Taken all together, the plant’s annual savings by reducing fossil fuel use in
their boilers and by eliminating off site waste disposal costs actually exceed the
operating costs of their new emission control system. Over its design life, the
DFTO system provides a net pay back to the plant, proving that “being green”
does not have to come at the expense of the bottom line.
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Complete DFTO system view
Author
Jon Hommes is an Engineer in the Environmental and Energy Systems
business unit of Dürr Systems, Inc in Plymouth, MI. He holds a B.S Ch.E. from
the University of Michigan in Ann Arbor.
As an independent business unit of Dürr Systems, Environmental and Energy
Systems is an innovative manufacturer of over 4,000 systems for air
purification worldwide. For more than 40 years, Dürr’s environmental
technologies have provided clean air and reduced emissions for a wide variety
of industry.
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